6 Phosphazenes

BY C. W. ALLEN

2 Introduction

This chapter covers the literature of phosph(V)azenes with reference to lower valent species when they can be transformed, or otherwise related, to the phosphorus (V) species. The interest in these materials by both academic and private sector chemists has insured a steady flow of papers and patents. There have not been any global reviews and in keeping with previous practice highly focused reviews will be cited in the appropriate sections below.

2 Acyclic Phomhazenes

Numerous reviews of acyclic phosphazenes (phosphoranimines, phosphine imines, iminophosphoranes, phosphazo derivatives) have appeared. These include a comprehensive review of the preparation, properties, MO calculations and reactions of the imines of phosphorus’, the utilization of (vinylimino) phosphoranes in the synthesis of nitrogen heterocycles2, four- membered heterocycles from iminopho~phoranes~ and 1 inear and cyclic phosphoraniminato complexes are mentioned in a review of metal nitrido complexes4. Ab initio calculations on several small phosphorus-nitrogen fragments are available. Of the three isomeric forms of PNHX, the nitrene, H(X)P=N, has the shortest phosphorus-nitrogen bond5. The rearrangement of MeP(0)NH2- to MeP(O)H(=NH)- is predicted to be exothermic while the reverse pathway is favored for MeP(S)NH,-. structures and relative conformational energies were computed6.

Rotational barriers,

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

6: Phosphazenes 275

The potential energy surface for protonated PN has been explored with N-protonation found to be favored'. stabilized on the sulfur center'. N3-,PnH (n=l-3) have been examined and the R bond energy of PN is less than that of NN but more than PP'. Calculations on the model compound [Ta(NPH,),]* reproduce the structure and approximate bond lengths in the NPPh, complex".

(MNDO) calculations of the potential energy in Cl,PNP(O)Cl, (X=O,S) and (C13PNPC13)+ show that s-trans isomers in approximately eclipsed forms are most stable. The calculated rotational barriers were found to be low". Similar calculations show a stable trans-cis conformation for C1,PN (C1,PN) POC1, and [ C13PN ( C1,PN) ,PC1,]'PC1,'2. A variety of physical methods have been applied to the study of acyclic phosphazenes. Due to its wide utilization as an ltinnocentll counter ion, reports of the Ph,PNPPh,' (PPN+) cation have not been routinely covered in this series. A recent study of employing uv/vis, IR and NMR spectroscopy indicates that there is a detectable amount of charge transfer between PPN' and ($-C,H,) Cr (CO) ,PEt,- thus the PPN' cations should not be assumed to always be a non-interacting counter ion',. The molecular structures of the (C1,PN) ,PC1* cation with C1- and PC1,- counter ions have been carefully determined and the PN distance in the C1,PN unit is significantly shorter than that observed for (NPCl,),. Despite cationic geometrical variations, the electron density distribution in the two salts is similar',. The absorption spectrum of PN has been determinedusing synchrotron radiation and 16 new states have been uncovered. The observed Rydberg series converge to 11.83 eV15. spectra of monophosphazene thiourea derivativesshow solute/solvent interactions and physical constants such as pKa and heat of formation have been determined',. including depolarization data, and normal coordinate analyses for C1,PNP (X) C1, (X=O, S) and C1,PNPC1,+ll and C1,PN ( C1,PN) ,P0Cl2 along with [ C1,PN (C1,PN) ,PCl,] PC1, (n=1,2) l2 are available. isolated lo7Ag(PN) has been studied by ESR spectroscopy and local density calculations.

The proton in PNSH' is The linear and cyclic forms of

semiempirical

The electronic

Raman spectra,

Matrix

Strong Ag to phosphorus covalent bonding

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

276 Organophosphorus Chemistry

via metal to PN (isoelectronic with CO) A* bonding interactions occur17. for the formation of the R radicals arising from the homolytic dissociation of (Et,N),PR=N(CN),NC(CN),N=PR(NEt,), (R=Et,N,Ph)". Variable temperature 31P spectra for C1,PN (C1,PN) .P0Cl2 show coalescence at 220'k due to low barriers of rotation about the PN bond',. C1,PN(C1,PN),~lP(0)C12 spectroscopy and the C1,PN group reactivity has been shown to increase with n19. resulting from the rapid intramolecular isomerization of %P(SnMe,)=NSiMe, to %PN(SiMe3)SnMe3 (R=Me2CH) allows for determination of activation parameters2'. The equilibrium mixture composition and thermodynamic parameters of the RR'PN(Si%2)T3/RR'P(q3)=NSi%2 (M=Ge,Sn) system has been determined by 31P NMR spectroscopy and correlated to structural parameters21. rearrangement has been examined by GC-Mass Spectrometry and found to follow an intermolecular mechanism which can be catalyzed by BF3-OEtF. The gas phase ion chemistry of (%N),PN, (R=iPr) has been studied by mass spectrometry. In addition to azide loss, phosphazene cation, R(NH)P=N+, formation was noted2,. The bond polarity in 2 , 4 , 6 - (Me,C) ,C,H,N=P (R) =C (SiMe,) , has been determined from dipole moment measurement^^^.

ESR has also been used to get thermodynamic parameters

The rates of condensation reactions of Cl,PNP(O)Cl, to (n=1-4) have been followed by ,'P NMR

The 31P line shape analysis for the spectra

The rate of the (RO) ,P=NPh/ (RO) ,P (0) NPhR (R=Me, Et)

The preparation of acyclic phosphazenes can start from either phosphorus (111) or phosphorus (V) sources. The Staudinger reaction continues to be the most widely utilized approach'. Thus, the reaction of HN(PPh,), with Me3SiN, gives HN ( PPh,=NSiM+) 225 and (RO) ,P (S) N, (R=Et , Me) can be converted to ( EtO) ,P (S) N=PPh, or (MeO) zP (S) N=P (OEt) ,=PPh, from the appropriate phosphorus (111) derivative26. Treatment of diethyl-3- pyridylphosphite with PhN, gives 1 which undergoes a rearrangement to heating to give the pyridyl moiety with a -OP(O) (OEt)N(Et)Ph group in the 3 position27. RR'POSiMeJMe,SiN, (R=Ph, R'=Me,C) system gives an equilibrium mixture of RR'P(OSiMe,)=NSiMe, and RR'P(0)N(SiMe3)2 with the

The

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 277

OC Ph2FiAPph2 0 ./“i\N ‘ co /%

(3)

R” gRf

&‘(NEt2)2 NH

(4)

Me3C

CMe3 Ph

(9)

R R 0

PR3 I I PR3 II RC6H4 L A N = PPh3

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

278 Organophosphorus Chemistry

phosphoranimine tautomer being favored28. Addition of azides to phosphabenzenes gives 2 as presumed intermediates which undergo dimerization of the highly polar phospha~ene~~. reaction of 8-azidoquinoline with a coordinated phosphine in fac- Mo (CO) , ( CH3CN) PPh,PPh, gives the coordinated phosphoranimine 3,’. A series of patents describing the preparation of acyclic phosphazenes as monomers for chlorine free poly(phosphazenes) have In each a triorganosilylazide (most commonly Me,SiN,) is allowed to react with (RO),-,,( ‘RO) np31i34i39,

HOP(OR),37*38 to give the desired monomer.

The Staudinger

(R,N),- ,, (R’ N 1 (RS 1 ,-,, (R S 1 (RO 1 ,-,,R’,,P3’ , (RO 1 ,-,, (R, ‘N 1 np36a40 ,

Reactions of diamines such as Et,NCH2NEt, with phosphorus (111) compounds having an -NHR substituent proceeds with Et2NH elimination to provide a route to phospha~enes~’. ( EtO) zP (CH,NEt,) =NC ( 0 ) CH, , P h N H w yields Et2NCH2 (PhN=) POC,H,b which dimerizes on solvent removal and use of MeOCH,NEt2 allows for elimination of the trimethylsilyl group in (EtO),PN(SiMe,), give (EtO) ,P (CH,NEt,) =NSiMe;’. (Et,N),PNR gives, in addition to the major product (Et,N),P(S)R, the novel acyclic phosphazenes (Et,N) ,P (R) =NC (CN) ,C (CN) ,N=P (R) (NEt,) , and (Et,N) ,P=NC (CN) =NC (CN) ,Rb2.

bis (diethylamino) phosphinocyclohexane with PCl,, C,Cl, , NH, and

Thus (EtO) ,PNHC ( 0 ) CH, yields

The reaction of EtSCN with

The reaction of l-morpholino-2-

to

NaOH provides 4 4 3 . Phosphorus (v) reagents are also precursors to acyclic phosphazenes. of the powerful non-nucleophilic base, (Me2N) ,P=NP (NMe,) ,+BF4-, from PC1, and NH4C1 is available44. with PC1, gives Cl,P=NCCl=C ( CH,C1) PC1,* PC1- which , upon treatment with SO,, provides Cl,P=NCCl=C (CH,Cl) P ( 0 ) C1:’. Cl,CCl=NC ( 0 ) NHCMe, with PCl,/POCl, leads to Cl,CCCl,N=CClN=PCl, which upon treatment with formic acid provides Cl,CCCl,N=ClNHP ( 0 ) C1,46. with alkyl halides leads to PhC(O)N=P(OiPr),XR (X=0,S)47.

interaction of C1,bN (Ph) N=C (CF,) b with (EtO) ,PNHPh gives a mixture of products including Cl(PhN=)hN(Ph)PN=C(CF,)b. preparation from ClhN (Ph) N=C (CF,) b and PhN, leads to the

A safer modification of the synthesis

The reaction of acrylamide

Treatment of

The react ions of PhC ( 0 ) NP (X) (OiPr) ,-Na+ The

An alternative

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 279

dimerized (cyclodiphosphazene) product48. A variety of routes have been employed to prepare silylated derivatives of (H,NPPh,NPPh,NH,) +C1-. undergoes reaction with Me,NS iMe, to H,NPPh,PPPh,NS iMe, or H[N(PPh,NSiMe,),]. Me,SiMPPh,NPPh,N(SiMe,) , by the sequential action of n-BuLi and Me,SiC125. Low valent species also play a significant role in acyclic phosphazene synthesis. Iminophosphines, RP=NAr [R=Ph; 2,4, 6-Rf,C,H, (R'=Me,CH) : Ar=2,4,6- (Me3C) ,C6H2] , can be oxidized by sulfur or selenium to give RP(X)=NAr (X=S,Se). If R=CMe,, oligomeric materials (RP(=NAr)X],, bridged through the chalcogen atom, are obtained49. Addition of acetylenes to iminophosphines gives phosphacyclopropenes with excocylic phosphazene bonds ( 5 )

while addition of methylene oyclopropanes give spirocyclopropane derivatives ( 6 ) Cycloaddition chemistry of RP=NAr (R=Me, Et; Ar=2,4,6- (Me3C) ,C6H, leads to a variety of heterocycles with exocyclic phosphazene bonds. A reversible [4+1] self addition with aryl activation leads to 7 . Addition to E and Z-azobenzene leads to 8 and 9 respectively5'. The reaction of ClP=NAr (Ar= (MeC) ,C6H2) with Cp,ZrMe, ( Cp=q5-C5Hs) leads to Me2P ( ZrCp2C1) =NAr which undergoes mild thermolysis to Me2PN(Ar)ZrCp2C1 which in turn is hydrolyzed by trace water to Me2PN(Ar)H. Reaction of the zirconium substituted phosphazene with ROSO,CF,(R=H, Me) gives Me2P (R) NHAr+OS02CF3-52. reactions of (Me,Si),NP=ESiMe, (E=CH,N) which give acyclic phosphazenes has appeared. Addition of MeC(O)ZHC(O)Me (Z=CH,CMe,N) provides Me,SiEH(Me,SiN=) hC(Me) (OSiMe,) Z=C(Me) d while the addition of MeC(0)CH2CH2C(O)Me to the low valent species where E=N gives Me,SiNH(Me,SiN=) hCH(OSiMe,) CH,CH,C(=CH,) 6 , while reactions with HOCR,C=CR' or HC=CH,Cl followed by (Me3Si) ,NPMe, lead to Me3SiN=P ( OSiMe,) ( NHSiMe,) C (R) C=C=CH, or (Me3Si) ,N (Me,SiNH) PC=CCH,PMe,=NSiMe,. Other relevant reactions involve addition of HC=CCH,Cl which goes to Me,SiN=PMe,CH,C=CH which can be derivatized to Me,SiN=PMe,CH,C=CSiMe, or can add HC1 to give Me,siN=PMe,c~cMe~~. Photolysis of Me3C (Ar) P (0) N, leads to transient mixtures of ArP(0)=NCMe3 and Me3CP(0)=NAr which are

Reaction with KH yields H [ N (PPh,NH) ,] which

The bis-silylated derivative is converted to

A symposium paper summarizing a variety of

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

280 Organophosphorus Chemistry

quenched by the solvent (methanol) to give MeOP(O)(NHR)R'. The diarylazide, Ar,P(O)N, follows a similar pathway with the added complexity of insertion reactions at the ortho position of the aryl groups4.

The transformation of acyclic phosphazenes to other functionalities is a continuing area of interest. Certain of these have been described above. The aza-Wittig reaction is of value in construction of heterocyclic systems. Ring closure of 10 with ArNCO leads to bicyclic guanidines including chiral bicycle species5'. 2,3-dihydrofuran-2,3-diones give the 1,3-oxazin-4-ones (ll)56.

The reaction of 3,8-methano [ll] annulenone (or the 11 C1 derivative) with Ph,P=NC (R) =CH, (R=H, Ph) gives annulenes with fused pyrrole ringss7. The formation of an acyclic phosphazene is the central event in a one pot conversion of alkybromides to amines. The reaction sequence involves formation of the azide, conversion to the phosphazene, aza-Wittig reaction to give the imine which is reduced or hydrolyzed to the amine58#59. group functions as a protected primary amine in the synthesis of aminophosphinesa. (CF,) ,CHC (CR,CF,) =NN=P (OEt) , gives high yields of (CF,) ,CH ( CF2CF3) =NN=C (CF,) CF,X6'. nucleophilic base, Me,NC=P[N=P(NMe,),], in promotion of the addition ally1 or benzyl bromides to N-protected peptides has been reported6,.

Reactions in which the phosphazene unit is retained have centered around the synthesis of metal phosphoranimato complexes. The reaction of Me3SiNPPh3 with TaCls gives [Ta (NPPh,) ,]TaC16'0, analogous reactions with NbClS, VC1, in the presence of Ph,PO, WNC1, or WO,Cl, and MoNC1, lead to NbC13(NPPh3),63, VCl,(NPPh,) (OPPh,)&, [W(NPPh,),]C1,65 and [Mo ( NPPh3) 4] [MoNC13 ( NPPh,) 3 266 respectively. reaction occurs in the ReNC1dMe3SiNPh, system in which [ReNCl (NPPh2C6H,) 3 , (12) is formed by C-H activation of the phenyl group. (Ph,PNH,) C167.

A [4+2] cycloaddition of NCN=PPh, to 5-aryl-

The N=PPh,

The addition of CF3C(0)CF,X(X=C1,F) to

The use of the strong,

A more complex

The HC1 biproduct reacts with Me,SiMPPh, to form The reaction of W (NPR,) C1, (R=Me, Ph) with oxygen

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 28 1

Me3SiN=P, P = N Si Me3 0, /CI CI, /ON

C f I %I CI' I %I Mo-0-Mo

0 0 CI, I /Cl CI, I /CI

Mo-O-,M? ,O' %I CI 0-P=NSiMe3

6

I I I PhpP PPh2

I I I

R L

(15)

6

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

282 Organ op 11 osp ho r us Chemistry

atom sources, either adventitious HOCl or C1,O in reactions with C1, or deliberate addition of pyridine N-oxide, gives W(NC1)C14(OPR,). The intermediate coordination of pyridine N- oxide was detected by NMR spectroscopyM. The addition of Me,SiOPPh,NSiMe, to NbC1, and CpTiC1, yields 13 (M=NbCl,, CpTiC1) while (C,F,),P(Cl)=NSiMe, adds to MoO,Cl, and MeC1, to give 1 4 and (C2F5) ,P(Cl) =NMoOCl, re~pectively~~. describing the coordination chemistry of (CF,),AsN=PPh, (L), obtained from (CF,),AsN,/PPh,, with osmium carbonyls leading to Os, (CO) 1, .L and Os, (p-H) , (CO) 9 - L has appeared. indicates delocalization over the As=N=P unit7'. Numerous investigations of the coordination chemistry of R,P(X)NP(X)R,- anions (X=O,S,Se) have been noted. The reactions of Re((NMe)Cl,(PPh,), with MN(XPPh,), (M=H, X=O; M=K, X=S, Se) lead to Re(NMe)Cl,[N(XPPh,),]PPh, (X=O,S,Se) and Re(NMe)Cl[N(XPPh,),], (X=S,Se). Similar chemistry of ReNCl(PPh,), gives ReNCl [ N ( SPPh,) ,] PPh, and ReNCl [ N (XPPh,) ,] , (X=S , Se) 71.

crown-6 adduct of K[ Ph,P(O) NP(0) Ph,] has been described7'. thiolato complexes Pd[ (PhO),P(S)NP(S) (0Ph),lT3, Me,Sn [ ( S ) PPh,NPPh, ( S ) ] 74 and Me2Sn [ ( S ) PPh,NPPh, ( S ) 3 274 have been prepared and characterized. Systematic studies of the solvent extraction capabilities of imidotetralkylpyrophosphates, suggest considerable potential in this system. Synthesis and formation constants of the protonated form of the ligandE, extraction of lanthanide ions76 and interactions with nitric acid77 have been studied.

The full manuscript

X-ray data

The 1 : 1 18- The

Applications other than those noted above, e.g. organic synthesis, solvent extraction, etc, have been noted. The carbonylation of MeOH to AcOH is improved by use of [Rh(C0)2C1]2 as a catalyst in the presence of [ (NH2) Ph,PNPh, (NH,) ]C1 as a promoter7'. The formation of high viscosity poly(dimethylsi1oxanes) can be effectively catalyzed by [ X (PX,=N) ,PX3] + (X=C1 , n=1-8) with counter ions such as AlC14-79,80. Agrochemical microbicide behavior is exhibited by Ph,P (X) NP (SR) Ph, (X=O , S ) 81. Fungicidal activity of diphenylphosphine amide derivatives such as Ph2P (X) NPS (CH,Ph) Ph,

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 283

has been noteds2.

3 CYClODhOSDhaZeneS

Reviews of cyclophosphazene chemistry include a comprehensive survey of recent advances in structure and reactions8,, cyclophosphazenes as ligands in coordination and organometallic chemistryu and a summary of phosphazene fluids, primarily persubstituted aryloxy and/or fluoroalkoxy systems, and their uses as fire-resistant hydraulic fluids, lubricants, pump oils and lubricating greasess5. performed on the model compound (NPH,), in various conformations. The stabilizing effect of phosphorus d orbitals is claimed to be responsible for the variety of conformations with a difference of 6.6 kcal between the lowest energy form (tub) and the highest form (saddle)". Iterative extend Huckel calculations on 1- pyrazolylphosphazenes such as 15 suggest that conjugative interactions between the pyrazolyl and phosphazene rings lead to quinoid deformations of the former which acts as a T donor and u acceptor. Similar calculations on the model compounds (NPH,), and N3P3H5C1 were also reporteds7. have also been applied to the hexakis (dibenzo [b,d] furan-2- yloxy) derivative (16) as well as its p-chlorophenoxy and 2- naphthloxy analogs. The HOMO and LUMO in each case are derived from the T and a* orbitals of the aryloxy entitym. Ramam spectra under high pressure conditions have been obtained for both forms, boat(K) and chair(T), of (NPCl,),. Transformation of T to K and K form phase transition have been observeds9. chemical shifts of the =PCl (OAr) centers in aryloxychlorocyclophosphazenes shift down field with increasing Ka of the parent aryl alcoholPo. anions (Z=o , m, p-C1 , Br- , p-NO, : p-Me) with (NPC1,) , under phase transfer conditions are all second-order in aryloxide". Detailed kinetic studies of the phase transfer (tetralkylammonium salts/borate buffer) reactions ArO- (Ar=4-C6H,NO,, 2, 4-C6H,(NO,), with (NPCl,), show that the mechanism can involve reaction in the

Ab initio calculations have been

Extended Huckel calculations

The 31P NMR

The rates of reaction of ZC,H,O-

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

284 0 rganop h osp h orus Chemistry

organic phase or at the interface”. reaction of triethylbenzylammonium nitrophenoxides with (NPCl,), and N,P,Cl,~,,L, ( L=OCH3C3B,IIH,0CH20-) show that the nitrophenoxide anions follow a Sn2(P) mechanism while reactions of ion pairs go through a synchronous transition state. A change from an associate to a dissociative pathway is observed with increased degree of nitrophenoxide substitutionp2. Thin-layer chromatographic separation coupled with polarographic detection of isomers of N,P,Cl,L where L=l,l‘-dioxy-2,2‘-binaphthyl and 2,2’-binapthyl and 2,2’-dioxy-l,lt-binaphthyl groups has been achievedp3. The absorption isotherms of water vapor on N,P,Cl,- x(CF3CH20)x(NMe2)2 (x=O,2,4) and N,P4(NHC4H,), are all similar showing several kinds of absorption sitesp4.

and 100% yields of the mixture, from which (NPCl,), can be extracted with 98% H,SO,, can be obtained9,. product of (R2N)2PN, (R=ipr) can be trapped with R’kP(NR,)NR‘N=i (R‘=CMe,) to give a four membered phosphorus-nitrogen ring with one endocyclic phosphazene unit (17). When (R’N=),PNR,‘ (R’=Me,Si) is used as the trapping agent, 17 forms but undergoes a 1,3 trimethylsilyl shift to give the cyclodipho~phazane~~. In

The kinetics of the

The classic synthesis of (NPCl,), (n=3-9) has been revisited

The photolysis

an unexpected cyclophosphazene synthesis, the Staudinger reaction of Me,SiN, with ClbN(Me)C(O)N(Me)C(O)h¶e leads to 18 which can be independently prepared from (NPCl,), and MeN[C(O)N(Me) While not strictly within the domain of interest of this chapter, a new synthesis of a cycloarsazene is worth noting. The reaction of HAsO, with (Me,Si) ,NH gives [NAs (OSiMe,) ,139,. derivatives , N3P, (OR) ,CN (R=Ph, CH,CF, , OCH,CH,OCH,CH,OCH,) are available from the reaction of KCN with the chlorophosphazene in the presence of 18-crown-6. converted to the trans tris-cyano derivative by the action of the KCN/Bu,NBr systemw. been given to the reactions of amines with halocyclophosphazenes. One of the NH bonds of urea undergoes substitution with (NPCl,),. Ring expansion to (NPCl,), also occurs in this system”’. chlorine atoms in spiro- N,P3C1, [ NH (CH,) ,O (CH,) ,NH] are completely

New pseudohalide

Trans-2,4, 6-N,P3 ( NMe,) $1, is

Less emphasis than in previous years has

The

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 285

displaced by morpholine”’. The dithiadiamines, H2N (CH,) ,S (CH,) ,S (CH,) ,NH, n=3 -6 , f orm the spirocyclic N,P,Cl,- [ HN ( CH2) ,S (CH,) .S (CH,) ,NH] derivatives. monosubstituted derivatives N,P,ClSNH (CH,) ?S ( CH,) ,S (CH,) ,NH, are seen in the ,’P NMR spectra. not lead to a substituted cyclophosphazenelo2. to transannular and spirocyclic derivatives, N,P,(OCH,CF,),L, have been devised. difunctional reagents (1,8-diaminonaphthalene; 1,3-diaminopropane; 2,2’-biphenol; 1,8-dihydroxynaphthalene, -lf3-propanediol and 2,2- dithiabiphenyl), the transannular derivatives, including the first from aromatic diamines or diols, are obtained. If the same difunctional reagent is allowed to react with (NPCl,), and the resulting product is derivatized with the trifluoroethoxide, the corresponding spirocyclic isomers are observed’03. dihydrazidophosphoric acid derivatives, PhO(S)P(NRNH2), transform (NPC1,) ,,, to the spirocycl ic N,P,Cl,,-, [ NHNRP (X) ( OPh) NRNH] (n=3,4 ; X=O,S; R=H, Me)’”. MeNHCH2CH,0H and aziridine leads to N3P3 (NC,H,) , (N(Me) CH,CH,O) . These, and related compounds, exhibit significant antitumor behavi~r”~. most widely studied cyclophosphazene derivatization routes. Phase transfer catalysis reactions have been optimized for the preparation of N,P,Cl,-, (OC,H,X) , (n=1-6 ; X=o , m, p-Br , C1 , p-NO,, Me , etc.). Electron withdrawing functions (X) on the aryloxide favor hexasubstitution while tetra and penta substitution is favored in other cases. NMR data has been obtained on all productsPo. of N,P, (OPh), (OC,H,-p-NO,), are obtained depending on reaction conditions employed in the addition of the nitrophenoxide to N,P, (OPh) $1,. also reported106. derivatives [ NP (OAr) ,] ,,, (Ar=C6H4-o-R, R=Me , Ph) have been prepared and characterized. The ortho substituents do not significantly effect the ring conformation on PN bond lengths in the tetramers relative to [NP(OPh) The reaction of (NPCl,),

The intermediate

The H2N ( CH,) ,S (CH,) ,S (CH,) NH,/N,P,Cl, does Synthetic routes

If 2 ,4-N,P3(OCH,CF,),C1, is allowed to react with

The

The sequential reaction of N3P3C16 with

The reactions of oxyanions continue to be among the

A non-geminal pathway is generally followed and 31P Different isomers

Reduction to two f orms of N,P, (OPh) , (OC,H,NH,) , was A series of ortho-substituted aryloxy

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

286 Organophosphorus Chemistry

with the 3-trienylmethoxide ion gives N,P,(OCH,k=CHSCH=C?H), which spontaneously rearranges to the phosphazane on isolation’”. The addition of alkali metal P-naphtholates gives N,P,C1,~,(j3-OCloH,) , (n=1-6). Individual members of the series have been isolated1”. The polyether derivatives, N,P, [ OCH, (CH,OCH,) nCH,OR], (n=2, R=C4H9; n=31 R=C12H15; n=41 R=C,H,C,H,,) have been prepared and shown to be strong complexing agents for alkali metal bromides and iodides”’. The synthesis of [NP(OC6H4C,H,CN) , I 3 , , and nematic liquid crystalline behavior of the trimeric derivatives have been reported’”. formation of N,P,X, [ OCH (Me) CH,O] (X=C1 , NMe,) has been noted. A spirocyclic structure was proposed based on NMR data. The asymmetric center in the spirocycle leads to observation of diastereotopic GPC1, centers112. bis (hydroxymethyl) -0-carborane leads to N,P,Cl, [ OCH,C,BloHl,CH,O] which is proposed to have a transannular bridging o-carboranylene unit”3. trimethylsilylmethyl derivatives of (NPF,), are available. The reaction of Me,SiCH,Li with N,P,F,Ph leads to 2 I 2 ’-N,P,F, (Ph) CH,SiMe, and 2,4‘, 4 -N,P,F,Ph (CH2SiMe,) (with geminal trimethylsilymethyl groups) while excess lithium reagent gives N,P,Ph (CH,SiMe,) ,CHSiMe,-. N,P,Ph (CH,SiMe,) by simple proton donors. Deprotonation back to the anion occurs upon addition Me3SiCH,Li. Reaction of 2 , 2 ‘ -

N,P,F, (Ph) CH,SiMe, with NaOCH,CF, gives N3P3 (Ph) Me (OCH,CF,) , : the analogous reaction of N,P,F, (Ph) ( CH2SiMe3) , gives N,P,Ph (CH,S iMe,) , (OCH,CF,) 31 14.

Increasingly, new cyclophosphazene derivatives are prepared via reactions of exocyclic groups on the preformed ring system. The para-aminophenoxy group is an often utilized functionally in this regard. The reactions of N,P, (OPh) (OC,H,-p-NH,) (n=3 6) with 3-nitro or 4-nitrophthalic anhydride give rise to the 3- or 4- nitrophthalimidophenoxy derivatives which are excellent precursors to fire-resistant polymers and resin^"^. chemistry utilizing 4-ethynylbenzoyl chloride or 4-ethynylphthalic anhydride lead to N,P, (OPh) , (OC,H,NHC ( 0 ) C,H,C=CH) , and 19 respectively. Thermolysis leads to matrix polymers exhibiting

The

The reaction of

The synthesis of a series of mixed phenyl,

The anion can be protonated to

Similar

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 287

high char yields and heat and fire resistant potentia1116. oxidation of N,P, (OC,H,Me) , with KMnO, gives the mixture N,P,(OC,H,CH,) 6-n(C6H4C02H) (n=2-6) containing at least four products’”. The hexa substituted 4-t- butylcarbonyloxyphenylphenoxy cyclophosphazene functions as a t- BOC protected acid-labile component for a chemical amplification resist system in which a variety of imaging techniques (deep-W, e-beam, etc.) have been employed118. The formation of carbon chain polymers with cyclophosphazene substituents has been an active subject of research in recent years. Considerable recent activity was noted in this area. Patents describing new systems with emphasis on the flame retardent potential have been filed. The reaction of p-divinylbenzene with R2NH (R=ipr) and (NPCl,), gave N3P3C15NRCH,CH,C,H,CH=CH, which undergoes vinyl addition p~lymerization”~. the resulting phosphazene methacrylate polymerized with the phosphorus chlorine bonds intact or removed by derivatization with oxygen or nitrogen bases’,’. phosphazene substituted polymers is demonstrated in the reaction of (NPCl,), with poly(p-vinylphenol)“’. have also appeared. (R=OCH,CH,),OMe, n=1-3) is solvent dependent. Solvent hydrogen bonding is the significant factor and even the kinetic order of the polymerization rate is effected. Viscosity of the polymers were also solvent dependent suggesting conformational differences. Copolymerization of the phosphazene monomers with styrene was also described122. The metal extraction abilities of the N,P,F$OC,H,CH=CH, (R=oligo (oxyethylenes) )monomers and polymers was studied. All derivatives coordinated Ag* successfully but only long chain R groups worked well for alkali metal ions123. The synthesis of organic polymers with cyclophosphazene end groups has been approached by two routes. The initiation of styrene polymerization with the azo compound [ N,P,Cl,OC,H,NHCO (CH,) ,CMeCNN=] , gave rise to poly (styrene) with phosphazene rings at both ends of the chain. The termination of poly(styryl1ithium) with (NPF,), also introduces a phosphazene

The

Methacylaryloxides can be added to (NPCl,), and

An alternative approach to

More detailed studies The polymerization of N,P,%OC,H,CH=CH,

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

288 Organophosphorus Chemistry

end group124. to thin hard films has been de~cribed’~’. The coordination chemistry of cyclophosphazenes also continues to be of interest&. The reaction of Cu(II) halides with dimethylpyrazolylphosphazenes, L(15, R=Me), gives rise to CuX,L and (CuX,),L(X=Cl,Br) which have been examined by x-ray crystallography, optical and ESR spectroscopy and cyclic voltammetry. The phosphosphazene acts as a tridentate ligand involving two non-geminal pyrazoyl units and the endocyclic nitrogen atom between the two exocyclic moieties’25. previously reported metallated (with BuLi, Etpg, Me3A1, Et,Zn) derivatives of spiro-N3P3C1, [ NH (CH,) 3O (CH,) ,NH] act as alkyl transfer agents’,’.

The photopolymerization of N3P3 [ OCH,CH,OC (0) CMe=CH,]

The

Commercial interest in cyclophosphazenes is demonstrated by the large number of patents and applications oriented publications involving these materials. In addition to the work described above, the following additional investigations should be noted. attention as flame proofing agents for cellulose based (e.g. rayon) and other fibers obtained from natural so~rces’~~~’~’. A study of the thermolysis of amidophosphazene treated rayon showed that the phosphazene increased dehydration and that mixed methoxy/amido derivatives underwent a phosphazene/phosphazane rearrangement which contributed to their effectiveness’28. Specific applications, including shrinkproof and flame retardency, to cellulose cotton’33 and silk134~135 have been established. chlorophosphazenes and terephthaloyl chloride to obtain heat and fire resistant rnaterial~’~~. Curable phosphazene resins, often derived from N3P3 [ OCH,CH,OC (0) CMe=CH, ] 6 , have been used for surf ace protection decorative board for door, floor etc, 144*148

source of durable printing plates and color transferred images’49 and basis of image-holding members for photosensitive layers15’. Other photographic applications of cyclophosphazene derivatives include antistatic silver halide film^'^'*'^^. devices imbedded in phosphazene matricies have been ~laimed’’~.

Amidophosphazenes have attracted considerable

Lignosulfates are modified by

Photoconducting

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 289

Oligoethylene side chain materials serve as solid solvents for alkali metal salts in solid batterie~'~~. Enhancement of curing of phthalonitride polymers'55 and epoxy resins'56 is accomplished using aminophosphazene derivatives. Composites based on carbon fibers impregnated with N3P3 (OC,H,OH) and formaldehyde have good mechanical, chemical and thermal proper tie^"^. Siloxane polymerization is catalyzed by cycloph~sphazenes~~~. Alkyoxy and aryloxycyclophosphazenes have been prepared for use as hydraulic fluids, insulating oils, and transmission oil^'^^-'^'.

4 CvcloDhosDha(thia)zenes and Related Chalcoaenides

This section includes ring systems with both phosphazene and thiazene (selenazene or tellurazene) components. Solid state 31P NMR spectra for 20 (E=S; X=P; R=Ph, Me, Et, n=2; X=S, R=N=PPh,, n=1), 21 (R=R'=Ph) and 22 (R=Ph) have been shown to correlate with the solution spectra. The 1,5 derivatives (21) have one principle tensor element responsible for the low field shift. Site symmetry differences give different shifts in 21 (X=P, R,=Et,) but not in the corresponding dimethyl derivative'02. reaction of Me,CS (=NH)NH, with Ph,PR' (R'=Ph, NHPPh,) gives Me3CkNPPh,NPPh,R'63. Much of the recent effort in this area involves metal coordination chemistry of cyclophospha(thia)zenes. The reaction of 22 with [Pt2(p-C1),(PEt,)4]2+ yields the cis- [PtC1(PEt3),*22]' cation while the analogous reaction with [ PtC1, (PEt,) , 3 , gives trans-PtCl, ( PEt,) -22. In each, coordination of 22 occurs y& the nitrogen atom adjacent to the phosphorus atom'&. Novel chemistry resulting from functionalization of the disulfide bridge in 20 (R=Ph, X=P, R,=Ph,, E=S). Reduction with Li [ Et,BH] gives the dianion 1, 5-Ph4P2N4S;- which can be methylated with Me1 to give 21 (R=Ph, R'-Me) or treated with metal complexes to give 23 (E=S, X=M$ where M=Pt, L=PEt,, PPh,; M=Ni, kdiphos) in which the phospha(thiazene) acts as a bidentate sulfide donor. Addition of CH,I, to 1,5-Ph4P,N4St- leads to 23 (X=CH,) which upon sequential treatment with n-BuLi and Me1 gives 23 (X=CHMe)l6'. Monodentate ligands can also be produced by the reaction of 1,5-

The

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

290 Orgumphosphorus Chemistry

”.+ p2p PF2

N; 4

P P N’

N N

Se,, Se

PEt3 I

CI- Pt - CI

CI -Pt - CI

(25)

I PEt3

Ph3P=N-

Ph2 Ph2

(23)

CMe3

- 1 i- AICIL

R CMe3

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosp huzen es 29 1

Ph,P,N,S2 (20) with alkyl lithium reagents to give Ph,P,N,S,R- (R=Me, Me$) which upon subsequent treatment with cis- or trans- [MCl,(PEt,),] (M=Pd, Pt) gives [MCl(PEt,),*Ph,P,N,S,R] (21: R=Ph, E=S, R'=alkyl and MCl(PEt,),). A significant rotation barrier about the M-S bond has been detected and measured using 31P dynamic NMR spectro~copy'~~. been produced. The R,P (=NS iMe,) N ( SiMe,) , , SeCl,, Se,Cl, mixture produces both the 1,5 isomer 2 0 (E=Se, X=P, R=Ph, Me, Et), and the 1,3 isomer ( 2 4 ) . These thermally labile species undergo decomposition react ions e . g . , 2 4 (R=Me) decays to [ N (PMe,NH,) 2] ,Se which has the phosphazene cation hydrogen bonded to a Se2- anion. At 25', 1,5-Ph4N,Se, (20) dissociates to two [Ph,PNSeN]' 5-7r electron radicals which can be monitored by ESR spectroscopy. Density function calculations on the model compound [ H 2 s N ] suggest that the SOMO is a p, orbital on selenium with no contribution from the phosphorus atom167. The coordination chemistry of 1,5-Ph,P2N,Se, has also begun to be explored. Treatment with [ PtC1, (PEt,) ,] , gives [ PtC1, ( PEt,) 3 , q'-N-Ph,P,N,Se, (n=1,2) in which the trans-PtC12 (PEt,) moiety is coordinated to one (n=1) or two (n=2, 25) ring nitrogen atoms. Oxidative addition of the 0'-complexes to Pt (C2H,) (PPh,) 1,023 (n=1 , 2 , E=Se, X=Pt ( PPh,) ,) la. The versatile Ph2P (=NSiMe,) N ( SiMe,) , reagent can be used to construct other rings e.g. interaction with RSeC1, (R=Ph,Me,Et) produces the 1,5 isomers, (E=Se, R=Ph, R'=Ph, Me, Et) , and a trace of 1,5-Ph,P2N,Se, ( 2 0 ) . The 1,5 dialkyl derivatives undergo a slow isomerism to the 1,3 isomer in the solid. The phenyl analog undergoes thermolysis at 140' to give Ph,Se, and (Ph,PN),,,. in toluene to give Ph,P(=NH)NH, and R,Se,. These mixtures react slowly at room temperature to give [Ph,P(NH,) 2]Se'69. derivative, Ph,bN(SiMe,) TeC1,RfJ (SiMe,) is available from Ph,P(=NSiMe,)N(SiMe,), with RTeC1,. formally phosphazenes, these materials are sufficiently relevant to be noted in this chapter17'. The reaction of (Cl,PNPCl,)+Cl- with Me3SiNSiMe3 gives P,N,SCl, (25) l7l,l7,. Reactions of 2 6 with oxyanions have been explored.

Selenium containing rings have also

1

All three 1,5 derivatives decompose at 110'

A tellurium (R=Ph, p-C6H,0Me, mesityl) ,

While not

Treatment with NaOCH,CF3 gives the

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

292 Organophosphorus Chemistry

persubstituted material, P2N3S (OCH,CF,) 5 . Reactions of NaOR (R=C,H,-p-CMe,, C6H,-o-C,H,) give P,N,SCl,OR with substitution occurring exclusively at the sulfur center. Subsequent treatment of P,N,SCl,OC,H,-p-CMe, with NaOC,H,-p-C,H, gives P,N,S ( OC6H,-p- CMe) (OC,H,-p-C,H,) ,171. Cyclothiazenes with exocycl ic phosphazene units have also continued to attract attention. The reaction of (amino) diphosphines, R (Ph) ,P, with S,N, leads to R (Ph) ,P=NSNSNSN or 1,5-[Ph,PR=N],S,N, depending on the reaction stoichiometry. The 1,5 isomers all are transformed to the R(Ph),P=NS,N, systems in solution at room temperatureln. The corresponding reactions of diphosphines Ph,PXPPh, (C=NC,H,N, CH2CH2) gives I&iii&N=PPh,XPh,PN=Ng"SN , Ph,P (S ) CH2CH2 (Ph) ,P=NB"SN and Ph,P (S) NC,H,NP ( S ) Ph,174. has also been explored. The (amino)diphenyl compounds undergo

-

The reactivity of Ph, (R) P=NS,N, derivatives

cycloaddition to norbornadiene at the 3,5 (relative to the phosphazene derivatized sulfur atom) positions. Treatment Ph3P=NS3N3 under similar conditions leads to 1,5 ( Ph3PN) $3,N,. R is a secondary amino derivative, Ph,(R) P=NS,N, decomposes solution to the Ph,(R)PNH,+ cation while the 2-pyridylamino species decomposes to 2 2 . Acid hydrolysis of Ph,(R)P=NS,N, Ph,P(O) OH175. &FCFCFCFCN=s=NSh with Ph,P leads via ring contraction to bFCFCFCFCN=S (N=PPh,) SC!lE.

The reaction of the o-C,F, derivative,

of When

in

gives

5 Miscellaneous PhosDhazene Containina Rinu systems

A decrease in activity in this area is noted for this reporting period. Metallocyclic systems have been covered in section 2 .

The reaction of PhhOCH2CH2hH with Et,NCH,NEt2 gives the monophosphazene Ph(Et,NCH,)h=NCH,CH,b which undergoes ring opening to EtOP(0) PhCH,NEt, upon addition of ethanolc1. The reaction of 4

with various main group halides leads to monophosphazenes e.g. p- Me,NC,H,PCl, gives 27 (E=lone pair, R=C,H,NMe,) which can be oxidized to 27 ( E = O ) . In similar fashion MeP(O)Cl, gives 27

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 293

E=O,R=Me and Me2Sicl, gives a heterocycle related to 27 with the P(E)R unit replaced by the SiMe, m0iet9~. (R=CMe3) to benzonitrile in dimethoxyethane (DME) gives the monophosphazene zwitterion (DME) 2LiN+=C (Ph) N=P (R) ,C- (Ph) which upon treatment with methanol gives fi=C(Ph)N=P(R),c(Ph)H'n. Nitrile addition is also observed in the reactions of RCN (R=Me, ipr, Ph) to Me,P(ZrCp,),=NAr which gives the five membered metallamonophosphazene, Me2b=N(Ar) Zr(Cp2C1) N=&R5,.

alkynes RC=CR' to the heteroatom triple bond in the phosphazyne cation (PSNAr) +AlCl,- (Ar=2,4,6- (Me3C) 3C6H2 is a route to novel monophospha(III)zenes, via the N-protonated salts 28 which can be deprotonated to the neutral form. The cycloaddition of CH2=CMeCMe=CH2 to 28 leads to saturation of the phosphazene by spirocycle formation at the phosphorus centerln.

Addition of Lip%

Addition of

6 P o l Y tDhosDhazenes)

This section covers polymers derived from open-chain phosphazenes and related cross-linked materials. Cyclolinear and cyclomatrix materials as well as carbon chain polymers with cyclophosphazene substituents are covered in section 3. Reviews involving poly(phosphazenes) include: transition metal and organometallic complexes84, synthesis by substitution reactions of poly (dihalophosphazenes) to generate materials with properties such as elasticity, ionic conductivity, non-linear optical or liquid crystalline behavior and biological app1icationslm, mechanism of cyclophosphazene polymerization including role of catalystslm, synthesis of ceramic materials from cyclic and polymeric precursors'", synthesis of phosphazene polymers and elastomers'@, and poly(ph0sphazene) photochemistry'". Shorter summaries in less accessible sources include gas transport in poly(alkoxyphosphazenes)'84 and current work in applications directed synthese~'~~.

precursors remains an important synthesis route. A patent describes the use of mixtures of P(O)Cl, and oligomeric

The formation of poly(phosphazenes) from small molecule

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

294 Organophosphorus Chemistry

cyclophosphazenes, (NPCl,),, to give short chain species with a Cl,P(O) end group which upon heating are converted to the high polymer’”. increases for short chain species but levels of f with longer chains”. examined by Mossbauer, IR and NMR spectroscopy. Redistribution of phenyl groups and chlorine atoms between the organotin reagent and the propagating species was established. Regulation of molar mass and yield of the polymer was dem~nstrated’~~. of the behavior of transannular bridged ( 2 9 ) vs. spirocyclic ( 3 0 )

cyclophosphazenes under thermal polymerization conditions showed that 2 9 (RX2=m-phenylenedioxy; 1,8-napthylenedioxy; 1,8- napthylenediamino) underwent ring opening polymerization to low molecular weight poly (organophosphazenes). The transannular 2,2’-biphenyldioxy ( 2 9 ) and all the spirocyclic ( 3 0 ) analogs of the polymerizable derivatives of 2 9 gave ring expansion products (tetramer to dodecamer) instead’=. The transannular bis(hydroxymethy1)-o-carborane tetrachlorocyclotriphosphazene also has been reported to undergo phosphazene ring opening p~lymerization”~. Heterocyclophosphazenes undergo ring opening polymerization e.g. the thiophosphazene Cl&NPCl,NPCl,k can be polymerized at 90’. The reactions of [ (NPCl,),NSCl], with aryloxides leads to initial displacement of the chlorine atom bound to the sulfur center followed by reactions at the =PC1, centers. The role of steric effects is clearly seen when the three (o,m & p) NaOC,H,C6H4 reagents are examined in that with the ortho derivative only half the P-C1 bonds are displaced while in the para derivative complete substitution occur.^^^'^^^^. opening polymerization of X(O)&NPCl,NPCl,h (X=F, C1) also has been accomplished. with NaOAr (Ar=Ph, C,H,C,H, , C,H,CMe,Ph , C,H,-m-CF,) occur exclusively at the EPC1, centers to yield [ (NS (0) X) (NP(0Ar) 2)2]n189~190. IR, DSC and light scattering has been obtained’89. Additional derivatives with alkoxy and alkenyloxy substituents, the latter being cross linkable, have been obtained’”. A patent describing

Kinetic studies show that the condensation rate

The Ph,Sn catalyzed polymerization of (NPCl,), has been

A comparison

The ring

Reactions of the polymer, [ (NS (0) X) (NPC1,) ,] ,

Characterizational data using NMR,

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 295

the polymerization of ClhNPCl2NPCl2k and derivatization of the resulting polymer to [CR(NPR2)2], (R=OPh, NHPh) is available19'. Several patents describing the catalyzed conversion of (CF,CH,O) (RO) ,(R'O) 2-nPNSiR1R2R3 to the chlorine free poly(organophosphazenes), [(RO)(R'O)PN],, under mild conditions have Catalysts employed include BU,NB~~~', alkali metal f l~orides'~~, BuLi19', RONa195 and NH,F'". reaction has been used to generate hybrid organic/phosphazene polymers by the reaction of C12PCH2CH2PC1, with p-diazidobenzene which gives [ =NC6H,N=PC1,CH2CH2PC12=] ,. CH, (OCH,CH,) .ONa (x=2,7,12,16) gives polymers with polyether side chains. Doping with lithium triflate gives materials with solid state conductive significantly greater than the analogous PEO systems but less than the poly(ph0sphazenes) with polyether side chains (MEEP)197. Phosphorus nitrides, while not strictly phosphazenes, are of interest in this section. The ammonolysis of C1,SiN=PC13 gives [SiPN(NH2)3-, (NH2)2]x, a cross linked polymeric imide with phosphazene units in the chain. Heating to 800' gave SiPN, which has a structure built of PN, and SiN, corner sharing tetrahedra. The interaction of Ca,N, and P,N, at 800' gives Ca2PN3 which consists of chains of corner sharing N, tetrahedralw.

is the reaction of (NPCl,), with nucleophiles. Polyalkylether derivatives [ NP (OCH,CH,OR) 2] [ (R=Me (MEEP) , CH20C,H9, CH,CH,OMe, CH,CH,OEt, CH,NH,] are available from NaOCH,CH,OR and are converted to hydrogels by y irradiation. The water solubility behavior of the linear and crosslinked polymers was examined"'. with five membered heterocycles (pyrrole, thiophene and furan) side groups linked to the phosphazene through various alkoxy chains have been prepared. to oxidation to dark blue powders which exhibit semiconductor behaviorlm. prepared by reaction of the alkali metal fluoroalkoxide with (NPC12),. explored2l'. Mixed alkylaryloxide/fluoroalkoxide derivatives

The Staudinger

Reaction with

Increased temperature leads to Si,N,/P,N2198.

Another major route for the synthesis of poly(ph0sphazenes)

Polymers

Doping with Fe(C10,), or FeC13 leads

Fluoralkoxy derivatives with crystalline content are

The role of temperature and solvent polarity was

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

296 Organophosphorus Chemistry

which are rubbery materials with high elongation are also available from the macromolecular substitution route202. Chloralkoxy derivatives are obtained from the reaction of ethylene oxide, or its derivatives, with (NPCl,), in the presence of AlC1,. glass expoxy on polyester composites was demonstrated and interestingly no correlation between phosphorus or phosphorus plus chlorine content and activity was noted2”. Phenylazophenoxy derivatives have also been reported to be active in reaction with (NPCl,) ,loo. Cyanophosphazenes are obtained when (NPR,.,Cl,,,) (R=OPh, We,) are allowed to interact with KCN in the presence of 18-crown-6. The resulting cyanophosphazenes retained some residual chlorine atoms. Reaction of the phenoxy/cyano derivative with NaOPh gave [NP(OPh)2]n while treatment of the dimethylamino/cyano species with dimethylamine provided

[NP(NMe2) 1.7(CN)0.3]nw. poly(fluoropheny1phosphazene) followed by NaOCH,CF, gave

[ NPPh,,, ( OCH2CF3) ,.66-x (CH,SiMe,) but the effect can be limited by careful control of reaction conditions. As the Me3SiCH2 content increased, less weight loss was observed in the TGA suggesting that the organosilicon moiety was the site of crosslinking reaction’’,.

The reactions of preformed polymers can be extended to The oxidation

The flame retardent effect of these materials for

The reaction of Me,SiCH,Li with

,. Some chain degradation occurs

include side group modification chemistry. (KMnO,/NaOH) of [ NP (OC6H,-p-Me) ,] , and its y irradiated cross- linked films produces a -OC,H,CO,Na surface. surface modification has been characterized by contact angle measurements, SEM, TEM and IR and XPS spectroscopy. The sodium carboxylate can be transformed to other metal salts or converted to the free acid which in turn can be coupled to a tetrapeptide or reduced to the benzylalcohol. Acid chlorides react with the alcohol to give esters117. mole ratio is greater than one. degradation. followed by para attack204. protected by a trimethylsiyl group react with (NPCl,), to give 2-

The nature of the

Sulfonation of [NP(OPh)Z], with SOJPN Lower mole ratios lead to

The sulfonation occurs first at the meta positions Aminoalcohols with the alcohol

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phospharenes 297

(trimethylsiloxyl)ethylamino, 3-(trimethylsiloxyl)- propylamino and 2,3-(bistrimethylsiloxyl)propylam~no derivatives. Total C1 replacement was only achieved with the first two reagents. Glycine ethylester moieties can be added as cosubstituents. The free alcohols are available upon treatment with Bu4NF. hydrolytic degradation of the resulting water soluble polymers was s t ~ d i e d ~ ~ ~ ~ ~ ~ . Radical initiated grafting of maleic anhydride to [ NP (OC6H4-p-CH (CH,) C2H,) 2] has been accomplished. The grafted materials exhibit increased adhesion to an A1 surface207. Several organic polymers have been coated with MEEP and exposed to y

radiation to induce grafting. The modified surfaces were characterized by contact angle measurements and other surface specific techniques (ATR-IR, XPS, SEM). Addition of water gives surf ace hydrogelsZo8. Numerous polymers supported donor species including poly(phosphazene) derivatives have been evaluated for promotion of nucleophilic substitution reactions2w. monomers have been added to crosslinked networks of MEEP or [NP(OC,H,C(O)OC,H,),],. Radical polymerization resulted in formation of interpenetrating nets (IPN) of the inorganic and organic polymers2”. to poly(phosphazenes) suitable for biological applications. Water-solubilizing side chains allowed for polymers which inhibited growth of selected bacteria on the surface. Similar effects were noted in crosslinked MEEP hydrogels. Neither the active polymers nor their cyclic analogs showed mutagenic activity which suggest possible applications as coatings for implants2”. Poly(phosphazenes) with variable amounts of ethyl 2-(0- glycy1)lactate or ethyl 2-(o-alanyl)lactate substituents are hydrolysis sensitive and have potential as biodegradable materials2W#212. of the amino acid ester from the phosphazene followed by ester hydrolysis. All hydrolysis products are harmless213. These amino acid ester poly(phosphazene) derivatives can serve as matrixes for slow release of biologically active agents2O6s2I4. alkylating agent, melphalan has been studied in this regard and promising results using the leukemia L1210 model have been

The

Vinyl

Side group lIengineering*l is a useful route

The in vitro hydrolysis pathway involves release

The

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

298 Organophosphorus Chemistry

obtained214. Poly(phosphazene) matrixes have also been used for the controlled release of narciclasine (a potential antitumor agent)*15. Various phenoxy and amino poly(phosphazene) membranes have been evaluated as surfaces for cultivation of selected cell lines. Both adhesion and percent colony formation have been explored in detail for the [NP(OPh)2-x(NCH,H9)

measurements on poly(phosphazenes), certain of these, especially surface characterization, have been described above. The products of the hydrolytic degradation of alanine ethylester/imidazole substituted phosphazene have been identified by FAB-mass spectroscopy. The phosphazene fragments are all short chain P,N, linear species with varying degrees of amino acid ester (but no imidazole) substituents. The complete removal of side groups leaves (HO)2P(0)NP(OH)2NP(OH)3217. exposure of fluoroalkoxyphosphazene coatings on polyimide films to atomic oxygen has been examined using ESCA techniques. Both backbone rearrangement and scission of fluoroalkoxy side chains have been detected218. used to measure 0 1s binding energies in (NP(OPh),], cast films. The data has been compared to those from a variety of oxygen containing polymers'l'. Photochemistry of mixed isopropylphenoxy/benzoylphenoxy poly(phosphazenes) proceeds by intramolecular H atom abstraction from the isopropylphenoxy group by the excited benzophenone leading to photocrossing2". photolysis of the bis-(4-benzylphenoxy)phosphazene polymer occurs exclusively at the 2-benzylphenoxy group. degradation of polymer solutions occurs while no changes result from photolysis in the absence of 0,. undergo photocrosslinking with or without 0, being present221. Electrical and flow birefringence determination of electrooptical properties of bis (trif luoroethoxy) 222, f luoropr~poxy~~~ and f luor~amoxy~~~ phosphazenes gives Kerr constants showing high chain polarity due to the dipole moment of the monomer unit. data also indicates considerable chain coiling222.

Considerable attention has been devoted to physicochemical

The effect of

High resolution XPS spectroscopy has been

The

In the presence of 0,,

Films of the polymer

The Solid state

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 299

ionic conductivitieszz6 of poly(phosphazenes) with pendant 12- crown-4 etherzz5 or tetrazocyclotetradecanezz5 groups bound through alkoxy side chains have been m e a ~ u r e d ~ ~ ~ - ~ ~ ~ . The tetraza system is linked to phosphazenes at each nitrogen site giving matrix systemsZZS. In each case, synthesis is achieved by reaction of the crown ether or tetraazamacrocycle with [NP(OCH,CF,),],. In the crown ether system, the conductivity of IA salts as a function of the spacer between the crown moiety and the phosphorus center showed a maximum for the lithium salt with a methylene spacerzz4~zz6. salts (M=Mg, Ca, Ni, Zn) showed conductivity 2 orders of magnitude lower than PEO type systemszz5. The complex multiphase solid state behavior of poly(organophosphazenes) provides a rich area of physicochemical study. Several crystalline polymorphs of (NPMez) have been studied by x-ray d i f f r a c t i ~ n ~ ~ ~ ~ ~ ~ ~ . An orthorhombic form is obtained from dilute solution or from the supercooled meltzz7. crystalline forms, the monoclinic modification was the only one obtained upon melting and recrystallizationzz8. annealed sample of the orthorhombic forms shows two closely spaced endotherms (T(1) and Tm) and hence a narrow mesophase rangez27. Mesophases in ultrahigh molecular weight poly(ph0sphazenes) have been studied and various degrees of loss of positional order identified2z9. optical and x-ray studies of [NP(OR)z]n (R=Me, Et, i-pr, n-Bu, C5H11, C,H,,) allow for construction of a generalized phase diagram relating to the length of the alkoxy side chain on Tg, crystalline and mesophase formation. Interactions involving both main chain and side chains are important with mesophases only occurring with certain alkoxy chain lengthsz3'. A detailed DSC and x-ray study of [NP(OCHzCF3)z], shows two crystalline and one mesomorphic phase. One of the crystalline phase structures is controlled by side chain packing. In the mesophase only the main chain has regular packing. All three phases undergo reversible interconversion as a function of temperaturez3'. reorientation in the trifluoroethoxy derivative has been

The azamacrocycles complexed with Mz+

Other crystallization studies show two

DSC on an

Thermochemical analysis,

Structural

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

300 Organophosphorus Chemistry

demonstrated on samples submitted to biaxial stressz3'. component model for composites involving the trifluoroethoxy phosphazene has been developed and used to describe the dependence of the loss modules as a function of composition and temperature. Relaxation processes occur at the interface of the inorganic and organic polymers233. spectroscopic, thermal, optical and diffraction techniques have been applied to the study of phase behavior of halogenated phenoxy phosphazenes [ NP ( OC6H4X) 2 ] (X=F, C1 , Br; m and p) . group size affected Tg, T(1) and Tm in a fashion which seated linearly with T(l)/Tm. The semetic mesophase was primarily responsible for properties above T(l)234. The morphology and structures of these halophenoxy derivatives have been investigated. The thermotropic transitions are a linear function of substituent size. Globules of the polymers have been examined and the size has been shown to change with the heating and the increase ~rystallinity'~~. [NP(OC6H4-p-R)2Jn (R=Me, etc.; MeO; MeS) show that the mechanism involves a nucleation and a growth step. The crystallization rate depends on whether the change originates from the isotropic or mesophase state'36. polymers in the solid state has been explored in recent work involving poly (organophosphazene) blend^'^^-'^^. DSC and TEM measurements of phosphazene/vinyl polymer blends allow for understanding of side group interactions leading to miscibility of the two systems237. poly(vinylpheno1) with MEEP238g239 and [NP(OR) ' 3 , (R=CH,CF,, Ph) 238

has been explored. Only MEEP gave miscibility over the entire compositional range238. hydrogen bonding between the two components238i239. of a small amount of an acidic comonomer to styrene or methylmethacrylate polymers allowed for miscibility with MEESm.

has been the focus of several studies, most of which explore the potential of these polymers as selective membranes. The water absorption isotherm of [ NP (OCH'CF,) 2 ] , shows that the interaction

A three

A broad range of

Side

The kinetics of phase changes in

Interactions between two different

The potential miscibility of

DSC and IR studies showed a single Tg and Introduction

The interaction of small molecules with poly(phosphazenes)

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 30 1

is stronger for the polymer than any small cyclic molecules examined9,. Polymers with the composition [ NP (OR) (OPh) R=CH,CF, or C6H,Y where Y=SiMe3, Me,Ph, SiMePh,, Br) and [ N3P3 (OCH,CF,) ,, (0'-C,H,Fe] , have been characterized and the permeability of their films to 0,, N,, CO,, He and CH, examined structure - activity relations of substituent and permeability/selectivity were established and the role of crosslinking examined240. permeability and selectivity. The permeability was lower than that of silicones and selectivity could be related to gas/phosphazene interactionsz4'. Porous ceramic supports coated with [NP(OCH2CF3) z]n have strongly bonded layers and function as membranes in a variety of applications24z. [ NP (OPh) ,I, membranes received detailed s t ~ d y ~ ~ ~ - ~ ~ ~ . separation in aggressive waste-streams was probed using test pairs such as SOz/Nz, H,S/CH, and CO,/CH,. controlled process in these systems243. Liquid transport with clear relevance to contaminated ground water was also established. Using preevaporation techniques separation factors of 10,000 were achieved in the CH2C1,/H,0 system244. variation of gas permeation below T ( l ) on the bisphenoxy polymer gave Arrhenius plots which gave insight into factors controlling selectivity ratios','. employed in understanding diffusion and transport in these membranes246. Poly[bis(p-carboxyphenoxy)phosphazene] membranes have also shown excellent separation ability for chlorinated hydrocarbons and acid gasesz47.

poly(phosphazenes) is also of importance in any real understanding of the behavior of these polymers. Controlled polymerization of (NPCl,), from polycondensation of Cl,P=NP(O)Cl, allowed from preparation of a range of intrinsic viscosities of this material. These data were used to obtain Mark-Houwink coefficients in THF19. nathyloxy)phosphazene] gave an array of polymer sized which were studied by light scattering, viscometry and GPC. Mark-Houwink

, (x(2 ;

A membrane from ( NPMe,) , shows good gas

Several uses of Gas

Transport is a sorption

Temperature

Time dependent measurements have also been

Measurement of dilute solution properties of

Fractionation of poly[bis(p-

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

302 Organophosphorus Chemistry

coefficient determination allowed for estimation of molecular dimensions. Multiple 31P NMR peaks suggest branching and some =POH formation during polymer synthesis. The hydrolysis sites are proposed to lead to aggregation and hence molecular dimensions from light scattering which are larger than the viscometric data248. scaling law between radius of gyration and molecular weight has been applied to the 8-naphthyloxy phospha~ene'~~. The molecular dimensions agree with the experimental data248 and are interpreted in terms of intermolecular aggregation249.

[ NP (0 (CH,) ,Me) ,] scattering studies leading to Mark-Houwink constants and unperturbed dimensions. Combination with previous data in another solvent allowed for this analysis to be performed on polydisperse samples250. fractionated [ NP ( OC6H,C6HS) 2 ] samples has appeared. Various data analysis methologies were applied to determination of molecular dimensions. The chain conformation was semiflexible and progressed from a short rod to a long expanded coil as the molecular weight increased251. of [NP(OCH,CF,),], are combined in an investigation of polymer/solvent phase equilibria. Solutions of the polymer in ethylacetate/DMSO and acetone/DMSO are isotropic until the temperature is lowered and crystallization occurs forming crystallosolvate phases. Phase diagrams for these phases were prepared2,'.

confirmed by the high level of patent activity and other applications oriented publications. Some of these have been noted above. Fire retardency is a continuing interest area in cyclo- (section 3) and poly(ph0sphazenes) with meth~xy~'~ and p r o p o ~ y ~ ~ ~ systems being combined with polyolefins for fire resistant cable insulation. Polymeric electrolytes based on metal complexes of poly(phosphazenes) with Lewis base containing side chains e.g. MEEP are an important focus area for potential development. Battery systems give high energy density solid

A numerical procedure for evaluating the

Multiple samples of were subjected to viscometric and 1 ight

A detailed viscometric study of well

Solution and solid state studies

The commercial potential of poly(phosphazene) systems is

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 303

electrolyte^'^^, poly(phosphazenes) in electropolymerized polymers256, oligooxyethylene derivatives in the manufacture of double layer capacitor^'^' and non-flowing polymeric electrolytes derived from vinyl or sulfonate terminated ~xyethylenes~'~ have been reported. Oligooxylene systems serving as solid electrolytes useful for screen printing259 and electrochemical color display devices'" have also been noted. poly(phosphazenes) are central to construction of a gas diffusion oxygen cathode'61. Fluoroalkoxy phosphazenes are useful for gasoline, oil and heat resistant rubbers which can function in arctic conditions'62 as well for corrosive lubricant resistant seals263, and, when combined with ultrahigh molecular weight poly(ethylene), melt processable plastic compositions'&. Curable sites on the phosphazene are involved in aeronautical floor coverings265 and, when using a methacrylate substituent, applications for potting compounds or coatings2&. phenolic residues as cosubstituents in aminopoly(phosphazenes) introduces an antioxidant component to the polymers useful for adhesives, sealents or coatings267. Stationary phases for gas chromatography can be fabricated from fluoralkoxyphosphazenes'@. Fiber reeling processes involving fluoroalkoxy derivatives are improved by the use of endcapped polyether lubricant^'^^. Microbicidal coating involved Cu or Ag coated with poly(phospha~enes)~~~. application of poly(phosphazenes) as microencapsulating materials for eucaryotic cells, liposomes and sensitive proteins271.

Gas permeable

Placement of

Carboxylic acid substituents allow for

7 Crystal Structures of Phosphazenes

The following compounds have been examined by diffraction methods. All distances are in picometers and angles in degrees.

Comments

PN (central) 159.0(3)

PN (terminal) 154.3(2)

- Ref.

14

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

Organophosphorus Chemistry

PN (central) 157.5(2) 157.9(2)

PN (terminal) 150.2(2), 153.4(2)

NIPZ 154.1(6), N3P2 162.5 (8)

P4NS 166.q7) N3P4 156.3 (7)

25

P=N 155.7(3)

PN3 163.0(3)-166.0(3)

42

P=N 161.7(4)

PN3 162.1(4)-162.9(3)

42

(Me2CH)3C6H2P(S)= NC6H2(CMe3)3

5 (R=Me, R=C6H2(CMe3)3, R"=R=Ph)

49

50 PN 153.5(7), 157(1)

L PNC 142.2(6), 140(1)

5 (R=Et, R=C6H2(CMe3)3,R"=R"'=Ph) PN 152.0(4)

L PNC 143.5(4), 141.3(3)

50

6 (R=Me, R'=C6H2(CMe3)3, R"-Ph)

7 (R=Me, Ar=C6H2(CMe3)3)

PN=154.2(8), 153.4(6) 50

51 P=N 154.0(5)

PN (endo) 170.4(5)

PNC (Ar) 136.0(4)

P=N 155.9(5)

PN (endo) 151.q6)

PNC(Ar) 155.9(5)

51

31 (n=O) 272 PN 161.9(3)

1 PNN 108.9(2)

31 (n=2) PN 160.7(4)

L PNN 106.8(3)

272

PN 160.6(3)

L PNN 111.5(2)

272 Ph3PNNCPh2

3

pa(NPPh3)4]TaC16

PN (Av.) 159.5(4) 30

10 PN 153(2)-159(2)

154(2)-167(2)

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 305

L TaNP 149(1)-175(1)

13 (M=NbClj)*4CH3CN

( C F e N P P h 3

(18-Crown-S)kONPh2NPPh26

PN 160.2(5), 159.5(6)

L NbNP 156.4(3), 161.9(3)

PN 161.5(7)

VNP 161.4(4)

PN 156.4(8)-160.8(8)

LWNP 157.0(6)-163.3(5)

PN (cation) 159(1)-161.9(9)

PN (anion) 159.5(9)

f MoNP (cation) 149.9(5)-170.5(6)

L MoNP (anion) 138.0(5)

PN 164.1

PNH2 166.1

PN 163.1(3)

PN 156.4(10)

L AsNP 126.7(6)

PN 159.8(4)

L AsNP 135.4(9)

PN 157.7 (16)

LAsNP 133.0(8)

PN 157(1)-159.7(9)

r! PNP 126.0(6), 126.4(7)

PN 158.5(4), 159.2(4)

1 PNP 129.3(3)

PN 16532). 166.2(2)

PN 157.1(4), 156.8(4)

LPNP 1243

PN 158.2(7) 158.2(6)

67

69

70

70

10

71

72

73

73

14

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

306

15 (R=Me)

N4P4(H2Pz)g (analog of 15, R=H)

Nearly planar PN

PN (exo) mean 168.2

PN (endo) mean 157.7

close to planar

PN (exo) 167.6-168.5

PN (endo) mean 154.3

L NPN ex0 104.4

L NPN endo 123.3

N4P4(Me$’Z)8 (analog of 15, R=Me) less planar than R=H

PN (exo) 168.6-170.5

PN (endo) 155.7

L NPN (exo) 102.4

L N P N (endo) 121.3

2,2-N3P3Ph2(Me2Pz)4

16

17 (R=iPr, R=Me3C)

[(Me3Si0)2AN13

N3P3(0Ph)&N

Organophosphorus Chemistry

87

PN (exo) 168.1-170.3

PN (endo) 155.2-157.0

slight chair

PN (mean) 157.7(7)

L PNP (mean) 120.3(4),LNPP (mean) 117.8(4)

87

87

87

88

PN (endo) amine 165-166; imine 160 96

PN (exo) 165.6(1)-178.6(2)

slightly puckered

ASN 173.3(5)-175.3(5)

98

slight 1/2 chair 99

PN (Av.) 157.3, shortest to =P(CN)(OPh)

f. PCN 177.1(3)

slight boat

PNendo Av. 158.7

PN,, Av. 162.6

L PCN 176.0

2,2-N3P3C14(NH(CHd30(CH~20(CH2)3NH] non-planar N3P3

strong H-bonding in spin, loop

PNendo 158.3(7)-159.8(7)

PN, 163.3(7)-166.5(7)

99

101

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 307

2,2-N3P3C14[NH(CH2)2s(CH2)3S(CH2)2NH] planar N3P3

PNendo 150(2)-163(2) PN,, 158(2)-161(2)

30 (X=O, R=1,8-C10Hg)

trans-PtC12(PEt3)* 22 (R=Ph)

23 (X=CH2, E=S)

boat

PN 157.6(3)-159.2(3)

4 PNP 117.4(3), 119.2(2), 120.4(2)

1R boat

PN 156.6(6)-160.2(5)

L PNP 109.5(3), 117.6(3), 119.8(3)

planar

PN 156.9(4)-159.2(4)

L PNP 122.1(2)-122.8(3)

nearly planar

PN 156.7(5)-159.2(5)

L PNP 120.9(3)-121.7(3)

PN (Av.) 156.0,

L PNP 133.9, NPN 133.9

PN (Av.) 155.4, 155.5

L PNP 141.2, 135.8

L NPN 120.6, 120.9

PN(Av.) 157

L PNP 129.1,LNPN 120.9

102

103

103

103

103

107

107

107

PNendo (coord.) 159.3, (free) 157.3 126

PN, (Av.) (mrd.) 169.2, (free) 166.7

PN 159.2(3)-160.1(4)

L PNP 115.5 (Z), 117.5

f PNP 118.7

PN 160.9(15), 163.5(18)

L NPN 113.5(8)

PN 160.7(3)-162.0(3)

L NPN 118.2(3), 119.1(2)

163

164

165

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

308

PdC1(PEt3)2-Ph4P2N4S2Me

Organophosphorus Chemistry

166 PI-S binding

PN 161.5(3)-161.8(3)

L NPN 120.1(2), 119.7(1)

Phosphazene cation H-bonded to Se2- 167

P=N 158.4(3), PNH2 162.1(5)

L PNP 132.7(4)

PN 167.3(9), 164(1)

L NPN 110.9(4)

2s 168

PN 152.3(3), lS9.2(3)

L NPN 1u).8(1)

169 Zl (R=Ph, E=%, R'=Me)

6FCFCFCFN = S(N =PPh$i PN 1.494(5)

L SNP 136.2(3)

176

PN 162.2(4)

L NPC %.S(2)

177 (DME)+f'R2CPhNCPhd

(R=CMe$

PN 161.5(4)

L NPC %.S(4)

177

178

198

28 (R=R'-Ph)

SiPN3

PN 163(1)

Defect Wuaite structure

PN 165.8(20), 168.3(41)-173.0(25)

Ca2PN3 PN (terminal) 1625

PN (bridging) 167.4

199

orthorhombic form

cell dimensions

227

lbo modifications with chain

periodicity 490, S8Spm; cell

dimensions for first

228

231

23s

Three crystallines phases

monoclinic and orthombic phases

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes

References

309

1.

2. 3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

24.

IIYlides and Imines of Phosphorus" A. W. Johnson (Ed.), John Wiley and Sons, N.Y., 1993, Chapter 13, 403. M. Nitta, Rev. Heteroatom Chem,, 1993, % 87. P. Molina, M. Alafarin, C. Lopez-Leonard0 and J. Elguero, J. Prakt. Chem., 1993, 335, 305. K. Dehnicke and J. Strahle, & m e w. Chem.. Int. Ed. Enul., 1992, u, 995. 1992, 194. M. Perakyla, T.A. Pakkanen, J.P. Bjorkroth, E. Pohjala and H. Leiras, J. Chem. SOC.. Perkin Trans. 2, 1992, 1167. R. Glaser, C.J. Horan and P. E. Haney, J. Phvs. Chem., 1993, 97, 1835. G.M. Chapan, N.M. Klimenko and O.P. Charkin Russ. J. Inors. Chem. (Ensl. Tran ~1.1, 1992, 37, 97. G.M. Chapan, N.M. Klimenko and O.P. Charkin, Russ. J. Inoru. Chem. fEnsl. Transl.), 1992, 37, 102. D. Nusshaer, F. Weller, A. Neuhaus, G. Frenking and K. Dehnicke, 8 . Anoru. Alla . Chem., 1992, m, 86. D. Bougeard, C. Bremard, R. DeJaeger and Y. Lemmouchi, SDectrochim. Acta. Part A., 1993, m, 199. D. Bougeard, C. Bremard, R. DeJaeger and Y. Lemmouchi, J. Phvs. Chem., 1992, 96, 8850. M. Tilset, A.A. Zlota, K. Folting and K.G. Caulton, J. Am. Chew. SOC., 1993, 115, 4113. F. Belaj, Acta Crvstallosr.. Sect. B: Struct. Sci., 1992, MI 598. M. Brendohl, I. Dubois, D. Macau-Hereot and F. Remy, J. Mol. SDectrosc, , 1992, 156, 292. A.E. Arifien, Asian J. Chem., 1992, 4, 112 (Chem. Abst., 1992, 117, 8014n). J.A. Howard, R. Jones, J.S. Tse, M. Tomietto, P.L. Timms and A.J. Seeley, J. Phvs. Chem., 1992, 96, 9144. M.K. Kadirov, V.I. Morozov, R.M. Kamalov, G.S. Stepanov, A.V. Il'Yasov and M.A. Pudovik, PhosDhorus, Sulfur, Silicon Related Elem., 1992, 68. 247. G. D'Helluin, R. De Jeager, J.P. Chambrette and P. Potin, Macromolecules, 1992, 25, 1254. V.N. Torocheshnikov, M.V. Gurov, V.I. Mstislavskii, Yu. A. Veits, Yu. A. Ustynyuk and V.L. FOSS, J. Gen. Chem. USSR _(Enul. Transl.1, 1992, gQ, 116. M.V. Gurov, Yu. A. Veits, V.N. Torocheshnikov, D.E. Tsevtkov, A.L. Ilovaiskii, Yu Ustynyuk and V.L. FOSS, J. Gen. USSR I Enul. Trans1.l. 1992, 672, 116. U.A. Gilyarov, T.M. Scherbina, A.P. Laretina and M.I. Kabachnik, Bull. Russ. Acad. Sci.. Div. Chem. Sci. [Ensl. Transl.1, 1992, 41, 1931. A. Maquestiau, L.-2. Chen, R. Flammang, J.P. Majoral and G. Bertrand, Inoru. Chem., 1990, 29, 3097. A.S. Sherman, 1.1. Patsanovskii, E.A. Ishmaeva, A.V. Ruban, V.D. Romaneko and L.N. Markovskii, J. Gen. Chem. USSR IEnul. Transl.) , 1992, 62, 37.

H.G. Ang, W.L. Kwik and I. Novak, J. Chem. Re s., svnop - 1

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

310 Organ op h osp h orus Chemistry

25.

26.

27.

28.

29.

30.

31.

32.

3 3 .

34.

35.

36.

37.

38.

39.

40.

41.

42.

43.

44.

45.

46.

47.

48.

49.

R. Hasselbring, H . W . Roesky, M. Rietzel, M. Witt and M. Nottemeyer, PhosDhorus, Sulfur Silicon Relat. Elem., 1992, 72 , 209. L. Riesel and R. Helbing, 2. Anors. Allsem. Chem., 1992, 617, 148. P.P. Onys'ko, E.A. Suvalova, T.I. Chudakova and A.D. Sinitsa, J. Gen. Chem. USSR [Ensl. Transl.), 1992, 62, 473. M. Well and R. Schmutzler, Phosphorus. Sulfur Silicon Relat. Elem. , 1992, 72, 189. G. Markl, H. Sommer and H. Noth, Tetradron Lett., 1993, 34, 3107. A. Saravanamuthu, D.M. Ho, M.E. Kerr, C. Fitzgerald, M.R.M. Bruce and A.E. Bruce, Inors. Chem., 1993, 32, 2202. H. Suzuki and F. Okada, JDn. Kokai Tokkvo Koho, JP 04134086 (Chem. Abst., 1992, 117, 151159~). H. Suzuki and F. Okada, JDn. Kokai Tokkvo Koho, JP 04134089 (Chem. Abst., 1992, 117, 115160n). H. Suzuki and F. Okada, Jpn. Kokai Tokkvo Koho, JP 04139191 (Chem. Abst., 1992, 117,171690p). H. Suzuki and F. Okada, JDn. Kokai Tokkvo Koho, JP 04187691 (Chem. Abst., 1992 117 192076h). H. Suzuki and F. Okada, Jpn. Kokai Tokkvo Koho, JP 04178395 (Chem. Abst., 1992, 117, 2342562). H. Suzuki, S. Katayama and F. Okada, JDn. Kokai Tokkvo Koho, JP 04210695 (Chem. Abst., 1992, 117, 25156h). H. Suzuki, S . Katayama and F. Okada, Jpn. Kokai Tokkvo Koho, JP 04210697 (Chem. Abst., 1993, 118, 7191b). H. Suzuki and F. Okada, JDn. Kokai Tokkvo Koho, JP 04182493 (Chem. Abst., 1993, 118, 7187e). H. Suzuki and F. Okada, Jpn. Kokai Tokkvo Koho, JP 04120083 (Chem. Abst., 1993, 118, 7498g). H. Suzuki and F. Okada, J m . Kokai Tokkvo Koho, JP 04099785 (Chem. Abst., 1993, 118, 70516f). M.A. Pudovik, L.K. Kibardina, S.A. Terent'eva and A.N. Pudovik, J. Gen. Chem. USSR (Enal. Transl.), 1991, 61, 2293. R.M. Kamolov, G.S. Stepanov, L.F. Chertanova, A.A. Gazikasheva, and R.Z. Musin, PhosDhorus, Sulfur Silicon Relat. Elem., 1992, 68, 227. A.A. Tolmachev, A.N. Kostyuk, E.S. Kozlov and A.M. Pinchuk, J. Gen. Chem. USSR [Ensl. Transl.1, 1992, 62, 1255. R. Link and R. Schwesinger, Ansew. Chem., Int. Ed. Ensl., 1992, 31, 850. V.G. Rozinov, M. Yu. Dmitrichenko, V.I. Donskikh and G.V. Dolgushin, J. Gen. Chem. USSR (Encrl. Transl.), 1992, 62, 1574. Yu. I. Matveev and V.I. Gorbatenko, J. Gen. Chem. USSR fEnsl. Transl.1, 1992, 62, 262. N.G. Zabirov, F.M. Shamsevaleev and R.A. Cherkasov, J. Gen. Chem. USSR fEnsl. Transl.), 1992, 62, 876. S.K. Tupchienko, T.N. Dudchenko and A.D. Sinitsa, J. Gen. Chem. USSR [Ensl. Transl.), 1992, 62, 780. V.D. Romanenko, A.V. Ruban, A.B. Drapilo, A.N. Chernega and E.B. Rusanov, Heteroatom Chem., 1992, 3 , 181.

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphuzenes 31 1

50.

51.

52.

53.

54.

55.

56.

57.

58.

59. 60. 61.

62.

63.

64.

65.

66.

67.

68.

68.

70.

71.

72.

73.

74.

75.

76.

D. Banion, G. David, M. Link. M. Nieger and E. Niecke, Chem. Ber., 1993, 126, 649. E. Niecke, M. Link and M. Nieger, Chem. Ber., 1992, 125, 2635. A. Igau, N. Dufour, A. Mathius and J.-P. Majoral, Ansew. Chem., Int. Ed. Ensl., 1993, 32, 29. R.H. Neilson and K h . Angelov, ACS S ~ D . Ser.. 486 (PhOSDhOrUS Chem.), 1992, 76. M.J.P. Harger and P.A. Shimmin, J. Chem. SOC.. Perkin Trans.1, 1993, 227. P. Molina, M. Alajarin and A. Vidal, J. Ors. Chem., 1993, 58, 1687. D.D. Nekrasov, Yu. S. Andreichikov and O.A. Ratkin, J. Ors. Chem. USSR (Ensl. Transl.L, 1992, 28, 1041. N. Kanomata, K. Kamae, Y. Iino and M. Nitta, J. Ors. Chem., 1992, 57, 5313. T. Gajda, A. Koziara, K.K. Osowska-Pacewicka, S. Zawadzki and A. Zwierzak, Svnth. commun., 1992, 22, 1929. A. Koziara and A. Zwierzak, mthesis, 1992, 1063. S.-T. Liu and C.Y. Liu, J. Orq. Chem., 1992, 57, 6079. G.G. Bargamov, A.A. Kadynov and M.B. Bargamova, Bull. Russ. Acad. Sci.. Div. Chem. Sci. (Ensl. Transl.1, 1992, 41, 1277. T. Pietzonka and D. Seebach, Ansew. Chem., Int. Ed. Ensl., 1992, 3l, 1481. F. Weller, D. Nusshar and K. Dehnicke, Z. Anors. Allsem. Chem., 1992, 615, 7. T. Rubenstahl, K. Dehnicke and H. Krautscheid, Z. Anors. Allsem. Chem.. 1993, 619, 1023. E. Rentshler, D. Nusshar, F. Weller and K. Dehnicke, Z. Anors. Allsem. Chem., 1993, 619, 999. D. Nusshar, F. Weller and K. Dehnicke, Z. Anors. Allsem. Chem., 1993, 619, 507. D. Nusshar, F. Weller and K. Dehnicke, Z. Anorq. Allaem. Chem., 1993, 619, 1121. J.D. Lichtenhan, J.W. Ziller and N.M. Doherty, Inorcr. Chem., 1992, 3l, 4210. P. Olms. H.W. Roesky, K. Keller and M. Noltemeyer, Z. Naturforsch., B: Chem. Sci., 1992, 47, 1609. H.G. Ang. W.L. Kwik, Y.W. Lee and A.L. Rhenigold, J. Chem. SOC., Dalton Trans., 1993, 663. R. Rossi, A. Marchi, L. Mawelli, L. Magon, M. Peruzzi, U. Casellato and R. Graziani, J. Chem. SOC., Dalton Trans., 1993, 723. R. Cea-Olivares and M.A. Munoz, Monatsch. Chem., 1993, 124, 471. M. Nouaman, Z. Zak, E. Herrmann and 0. Navratil, Z. Anors. Allsem. Chem., 1993, 619, 1147. I. Haiduc, G. Silvestru, H.W. Roesky, H.-G. Schimdt and M. Noltemeyer, Polvhedron, 1993, 12, 69. J.G.H. DuPreez, K.U. Knabl, L. Kruger and B.J.A.M. Van Brecht, Solvent Extr.Ion. Exch., 1992, 10, 729. J.G.H. DuPreez, L. Kruger and N.M. Sumter, Solvent Extr. Ion Exch., 1992, 10, 749.

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

312

77. 78.

79.

80.

81.

82.

83.

84.

85.

86.

87.

88.

89.

90. 91.

92.

93.

94.

95.

96.

97.

98.

99.

Organophosphorus Chemistry

N.V. Jarvis, Solvent Extr. Ion Exch., 1993, 11, 223. R.G. Cave11 and K.V. Katti, WO 9204118 (Chem. Abst., 1992, 117, 113995f). J.M. Gilson and J.d.l.C. Habimana, Ger. Offen., DE 4205201 (Chem. Abst.. 1993, u, 39598f). J.M. Gilson and J.d.1.C. Habimana, Ger. Offen., DE 4205200 (Chem. Abst., 1993, 118, 39599g). H. Ishikawa, T. Umeda, Y. Kid0 and K. Kajikawara, JDn. Kokai Tokkvo Koho, JP 04164089 (Chem. Abst., 1992, 117, 1866460). H. Ishikawa, Y. Kido, T. Umeda and H. Ohyama, Biosci., Biotechnol., Biocfiem., 1992, 56, 1882. V. Chandrasekhar and K.R. Justin Thomas, Struct. Bondinq (Berlin), 1993, B l , 41. V. Chandrasekhar and K.R. Justin Thomas, ADD^. Orqanomet. Chem., 1993, I, 1. R.E. Singler and M.J. Bierberich, Chem. Ind. (Dekker) 48 (Synthetic Lubricants and Hiah-Performance Functional Fluids), 1993, 215-28 (Chem. Abst., 1993, 118, 215986s). D.H.R. Barton, M.B. Hall, 2. Lin and S.I. Parekh, J. Am. Chem. SOC.. 1993, 115, 955. K.D. Gallicano, N.L. Paddock, S.J. Rettig and J. Trotter, Can. J. Chem., 1992, 70 , 1855. G. Bandoli, M. Gleria, A. Grassi and G.C. Pappalardo, J. Chem. Res., Swnp., 1992, 148. D. Victor, S. Muthu, N. Chandrabhas, A.K. Sood, K. Venkatesau, P. Venugopalau and A. Jayaraman, J. Raman SDectrosc., 1992, 23, 611. Y . W . Chen-Yang and B.D. Tsai, Polyhedron, 1993, l2, 59. A.A. Afon'kin, A.E. Shumeiko and A.F. Popov, J. Gen. Chem. USSR (Encrl. Transl.), 1992, 62, 2097. A.A. Afon'kin, A.F. Popov, A.E. Shumeiko and Zh.P. Piskunova, J. Gen. Chem. USSR, (Enul. Transl.), 1992, 62, 892. B. Pasciak and A. Kozera, J. Planar Chromatour.-Mod. TLC, 1992, 5, 463 (Chem. Abst., 1993, 118, 182470~). P. Vassileva, L. Lakov, E. Gaheva and 0. Peshev, J. Mater. Sci. Lett., 1993, 12, 281. F. Zheng, 2. Wang, Z. Lin and H. Liang, Jilin Daxue Ziran Kexue Xuebao, 1992, 119 (Chem. Abst., 1993, 118, 2653431~). J. Boske, E. Niecke, B. Krebs, M. Lage and G. Henkel, Chem. Ber., 1992, 125, 2631. T.G. Meyer, P.G. Jones and R. Schmutzler, Z. Naturforsch.. B: Chem. Sci., 1992, 47, 517. M. Baier, P. Bissinger and H. Schmidbaur, Chem. Ber., 1993, 126, 351. H.R. Allcock, J.S. Rutt, M.F. Welker and M. Pawez, Inorq. Chem., 1993, 32, 2315.

and G.S. Golldin, Zh. Prikl. SDektosk., 1992, 56, 734 (Chem. Abst., 1992, 117 112222q).

Bonnet and J.F. Labarre, J. Mol. Struct., 1992,

100. S.V. Sin'ko, S.G. Fedorov, G.S. Nikitina, V.P. Voloshenko

101. R. Enjalbert, J. Galy, S . Schneidecker, D. Semenzin, J.P.

269,355.

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 313

102. R. Enjalbert, J. Galy, C. Galliot, S. Schneidecker, J.P. Bonnet and J.F. Labarre, J. Mol. Struct., 1992, 271, 95.

103. H.R. Allcock, M.L. Turner and K.B. Vissher, Inors. Chem., 1992, 31, 4354.

104. U. Diefenbach and U. Engelhardt, Z. Anora. Alla. Chem., 1992, 609, 67.

105. A. Duflos, J.F. Patoiseau, D. Rigg and R. Kiss, EP 482993 (Chem. Abst. , 1992, 117, 48917r).

106. D. Kumar and T . L . St.Clair, Polvhedron, 1992, 11, 1071. 107. H.R. Allcock, A.A. Dembek, M.N. Mang, G.H. Riding, M. Pane2

and K.B. Visscher, Inora. Chem., 1992, 31, 2734. 108. H.R. Allcock, J.A. Dodge, L . S . Van Dyke and C.R. Martin,

Chem. Mater., 1992, 4, 780. 109. K. Brandt, Pol. J. Am1. Chem., 1991, 35, 143 (-

1993, 118, 246297~). 110. M.P. Bullitta, E. Maccioni, L. Corda and G. Padda, J.

Heterocvcl. Chem., 1993, 30, 93. 111. M. Kajiwara, Annu. Tech. Conf.-Soc. Plast. Ena.. 49th, 1991,

1082 (Chem. Abst.. 1993, 118, 227489). 112. M.G. Muralidhara, N. Grover and V. Chandrasekhar,

Polyhedron, 1993 , 12, 1509. 113. M.P. Prigozhina, P.V. Petrovskii, L.G. Komarova and A.L.

Rusanov, Bull Russ. Acad. Sci., Div. Chem. Sci. (Ensl. Transl. 1, 1992, 4 l , 144.

114. H.R. Allcock and W.D. Coggio, Macromolecules, 1993, 26, 764. 115. D. Kumar, M. Khullar and A.D. Gupta, PhosDhorus. Sulfur

Silicon Relat. Elem., 1992, 68, 59. 116. D. Kumar, A.D. Gupta and M. Khullar, J. Polvm. Sci.. Part A:

Polvm. Chem., 1993, 3 l , 707. 117. H.R. Allcock, R.J. Fitzpatrick and L. Salvati, Chem. Mater.,

1992, 4, 769. 118. K.D. Ahn, J.H. Kang, S.S. Kim, B.S. Park, C.E. Park and C.G.

Park, J. Photopolvm. Sci. Tech., 1993, 5, 67 (Chem. Abst., 1992 , 117, 222896~) .

119. M. Imayoshi and K. Maeda, JDn. Kokai Tokkvo Koho, JP 04252208(Chem. Abst. 1993, 118, 125791~).

120. T. Tanigaki, K. Inoue, T. Inoue, J m . Kokai Tokkvo Koho, JP 04134090 (Chem. Abst., 1993, 118, 81629s).

121. M. Imayoshi and K. Maeda, JDn. Kokai Tokkvo Koho, JP 04252212 (Chem. Abst., 1993, 118, 60738m).

122. K. Inoue, H. Nakahara and T. Tanigaki, J. Polv. Sci., Part A: Polvm. Chem., 1993, 31, 61.

123. K. Inoue, H. Nakahara, K. Hisanori and T. Tanigaki, Makromol. Chem.. Rapid Commun., 1992, 13, 485.

124. K. Inoue, H. Takeda, M. Kogawa and T. Tanigaki, Kobunshi Ronbunshi, 1992, 49, 833 (Chem. Abst. 1993, 118, 102615b).

125. A. Yaguchi, S. Mori, M. Kitayama, T. Onda, A. Kurahashi and H. Ando, Thin Solid Films, 1992, 216, 123.

126. K.R. Justin Thomas, V. Chandrasekhar, P. Pal., S.R. Scott, R. Hallford and A.W. Cordes, Inors. Chem., 1993, 32, 606.

127. Fr. Demands, FR. 2673428 [Chem. Abst., 1993, 118, 255113).

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

314 Organ op hospho riis Chemistry

128. P.P. Novosel'tsev, M.A. Tyuganova, G.E. Krichevskii and M.V. Buyanova, Khim. Volokna, 1992, 28 (Chem. Abst., 1992, 117, 235732~).

129. T. Nakanishi, N. Wazuki and A. Maruyama, Jpn. Kokai Tokkvo Koho, JP 04057972 Chem. Abst., 1992, 117, 50723t).

130. T. Sasakura, Y. Anasako and Y. Hayashi, US 5108459A (Chem. Abst., 1992, 117, 71642t).

131. K. Morimoto, T. Nunoo and S. Ida, Jpn. Kokai Tokkvo Koho, JP 04333657 (Chem. Abst., 1993, 118, 214848m).

132. K. Morimoto, T. Nunoo and T. Ida Jpn. Kokai Tokkvo Koho, JP 04333672 [Chem. Abst., 1993, 118, 214849n).

133. P.P. Novosel'tev, M.A. Tyuganova, G.E. Krichevskii and M.V. Zaigrina, Izv. Vvssh. Uchebn. Zaved., Tekhnol. Tekst. Prom.- sti., 1991, 66 JChem. Abst., 1993, =, 126395f).

134. T. Sasakura, Jpn. Kokai Tokkvo Koho, JP 04316674 IChem. Abst., 1993, 118, 126459e).

135. Y. Hayashi and Y. Nomura, Jpn. Kokai Tokkvo Koho, JP 04316680 IChem. Abst., 1993, 118, 193605n).

136. H. Struszczuk and K. Wrzesniewska-Tesik, Cellul. Sources Exploit, Ed. J.F. Kennedy, G.O. Phillips and P.A. Williams, Horwood, London, UK, 1990, 505 (Chem. Abst., 1993, 118, 126722k).

137. M. Shigaraki and H. Yoshihiko, Jpn. Kokai Tokkvo Koho, JP 04159335 (Chem. Abst., 1992, 117, 152902t).

138. H. Ando, Jon. Kokai Tokkvo Koho, JP 03227463 (Chem. Abst., 1992, 117, 9928a).

139. R. Noshide and M. Shinoda, Jpn. Kokai Tokkvo Koho, JP 04203931 (Chem. Abst., 1993, 118, 170626f).

140. A. Kurahashi, Jpn. Kokai Tokkvo Koho, JP 04025564 (Chem. Abst., 1992, 117, 99643).

141. A. Yaguchi, JDn. Kokai Tokkvo Koho, JP 04132772 (Chem. Abst., 1993, 118, 40920m).

142. M. Yokoshima, T. Okubo and K. Sasahara, Jpn. Kokai Tokkvo Koho, JP 04225038 (Chem. Abst., 1993, 118, 82988~).

143. M. Wada and M. Yokoshima, Jpn. Kokai Tokkvo Koho, JP 04225026 (Chem. Abst., 1993, 118, 82993t).

144. A. Kozuka and K. Murahami, Jpn. Kokai Tokkvo Koho, JP 0412847 IChem. Abst., 1992, 117, 29114k).

145. A. Kozuka, Y. Ninomiya and K. Murakami, Jpn. Kokai Tokkvo Koho, JP 04012851 JChem. Abst., 1992, 117, 92553t).

146. A. Kozuka, Y. Ninomiya and K. Murakami, JRn. Kokai Tokkvo Koho, JP 04012848 (Chem. Abst., 1992, 117, 92552s).

147. M. Shiino, JDn. Kokai Tokkvo Koho, JP 04156331 (Chem. Abst., 1992, 117, 253517b).

148. Y. Aota and K.k Murakami, JDn. Kokai Tokkvo Koho, JP 04176647 JChem. Abst., 1992, 117, 252783~).

149. K. Kagami, M. Suzuki, T. Fukui and Y. Kondo, Jpn. Kokai Tokkvo Koho, JP 03282469 (Chem. Abst., 1992, 117, 140644~).

150. N. Ohtani, A. Maruyama, S. Nagahara and S. Mayama, Eur. Pat. Aptsl., EP 464749 (Chem. Abst., 1993, 118, 90766m).

151. K. Shirato and T. Yasuda, JJJ. Kokai Tokkvo Koho, JP 04149433 (Chem. Abst., 1992, 117, 222969~).

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 315

152.

153.

154.

155.

156.

157.

158.

159.

160.

161.

162.

163.

164.

165.

166.

167.

168.

169.

170.

171.

172.

173.

174.

175.

176.

K. Shirato, JDn. Kokai Tokkvo Koho, JP 04217240 (Chem. Abst., 1993, 118, 90732~). A. Kurahashi and A. Kageyama, Eur. Pat. ADD^., EP443626 (Chem. Abst., 1992, 117, 100917g). M. Takeuchi and R. Shishikura, JDn. Kokai Tokkvo Koho, JP 04301370 (Chem. Abst., 1993, 118, 84443n).

u, 9161~). S. Kubota, 0. Ito and Y. Maeda, Kenkvu Hokoka-Wakavam-ken Giiutsu senta, 1991, 37 (Chem. Abst., 1993, 118, 40047g). C.A. Allen, A.E. Grey, R.R. McCaffrey, B.M. Simpson and M. Stone, US Pat. ADD^., US 559234 (Chem. Abst., 1993, 118, 40531k). J.d.1.C. Habimana and S. Westall, EP 503825 (Chem. Abst., 1993, 118, 82140n). W.D. Klobucar and C.H. Kolich, US 5073284 (Chem. Abst., 1992, 117, 30270q). I. Kurachi, N. Kajiwara and T. Saito, JDn. Kokai Tokkvo Koho, JP 04198189 (Chem. Abst., 1993, 118, 81176s). I. Kurachi and T. Saito, JDn. Kokai Tokkvo Koho JP 04198190 [Chem. Abst., 1993, 118, 81177t). T. Chivers, M. Edwards, C.A. Fyfe and L.H. Randall, Masn. Reson. Chem., 1992, 30, 1220. D. Haenssgen, M. Jansen, A. Weidman and I. Mokros, Z. Anors. Allsem. Chem., 1992, 615, 49. T. Chivers, R.W. Hilts, I.H. Krouse, A.W. Cordes, R. Hallford and S.R. Scott, Can. J. Chem., 1992, 70, 2602. T. Chivers, M. Cowie, M. Edwards and R.W. Hilts, Inora. Chem., 1992, 31, 3349. T. Chivers, M. Edwards, R.M. Hilts, A. Meetsma and J.C. van de Grampel, J. Chem. SOC., Dalton Trans., 1992, 3053. T. Chivers, D.D. Doxsee and M. Pawez, Inors. Chem., 1993, - 32, 2238. T. Chivers, D.D. Doxsee, R.W. Hilts, A. Meetsma, M. Pawez and J.C. van de Grampel, J. Chem. SOC., Chem. Comm., 1992, 32, 1330. T. Chivers, D.D. Doxsee, J.F. Fait and M. Parvez, Inors. Chem., 1993, 32, 2243. T. Chivers and M.N. Sudheendra Rao, PhosDhorus, Sulfur Silicon Relat. Elem., 1992, 69, 197. H.R. Allcock, J.A. Dodge and I. Manners, Macromolecules, 1993, 26, 11. J.A. Dodge, I. Manners and H.R. Allcock, Polvm. Mater. Sci. Ena., 1992, 67, 412. C.J. Thomas and M.N. Sudheendra Rao, Heteroat.Chem., 1992, 3, 321. C . J . Thomas and M. N. Sudheendra Rao, Z. Anors. Allsem. Chem., 1993, 619, 433. C.J. Thomas and M.N. Sudheendra Rao, Z. Anors. Alluem. Chem., 1992, 615, 149. A.V. Zibarev, Y.V. Gatilov, I.Yu. Bagryanskaya, A.M. Marksimov and A.O. Miller, J. Chem. SOC.. Chem. Comm., 1993, 298.

T.M. Keller, U . S . Pat. Aml., US 670096 (Chem. Abst., 1992,

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

316 Organophosphorus Chemistry

177. G. Stieglitz, B. Neumuller and K. Dehnicke, Z. Naturforsch.

178. G. David, E. Niecke and M. Nieger, Tetrahedron Lett., 1992,

179. H.R. Allcock, NATO AS1 Ser.. Ser.E (Inora. Oruanomet. Polvm. Spec. ProD.1, 1992, 206, 43 JChem. Abst., 1993, m, 7408~).

180. H.R. Allcock, ACS Swn. Ser, 1992, 496, 236. 181. H.R. Allcock in "Chem. Process. Adv. Mater." L.L. Henck and

J.K. West (Eds.), Wiley, N.Y., 1992, 699-716 (Chem. Abst., 1992, 117, 218102r).

182. R. Dejaeger and P. Potin, Actual. Chem., 1992, 324 [Chem. Fbst., 1993, u, 255370t).

183. M. Gleria, P. Bortolus and F. Minto, NATO AS1 Ser.. Ser.E (Inoru. Oraanomet. Polwn. SDec. ProD.1, 1992, 206, 375 (Chem. Abst., 1993, 118, 7410~).

184. J.R. Fried, Chemtracts: Macromol. Chem., 1992, 3, 95 (Chem. Ab st., 1992, 117, 131794~).

185. C. Gong, S. Kuang and L. Tong, Xiandai Huaaonq, 1991, 11, 24 (Chem. Abst., 1992, 117, 49695d).

186. S. Bordere, P. Potin and R. Schneider, Eur. Pat. ADD^., EP 532396 (Chem. Abst., 1993, 118, 224393~).

187. V.Ya Rochev, Nucl. Instrum. Methods Phvs. Res.. Sect. B, 1993, B76, 17 (Chem. Abst., 1993, 118, 2554133).

188. H.R. Allcock and M.L. Turner, Macromolecules, 1993, 26, 3. 189. Y. Ni, A. Stammer, M. Liang, J. Massey, G. Vansco and I.

Manners, Macromolecules, 1992, 25, 7119. 190. I. Manners, M. Liang and A. Ostrowicki, Eur. Pat. Aml., EP

504694 (Chem. Abst., 1993, JJ&, 192538f). 191. H.R. Allcock, I. Manners, G. Renner and 0. Nuyken, US

5093438 (Chem. Abst., 1992, 117, 27531~). 192. H. Suzuki, S. Katayama and F. Okada, JDn. Kokai Tokkvo Koho,

JP 04296329 (Chem. Abst., 1993, 118, 2347342). 193. H. Suzuki, S. Katayama and F. Okada, J m . Kokai Tokkvo Koho,

JP 04314735 (Chem. Abst., 1993, 118, 234736b). 194. H. Suzuki, S. Katayama and F. Okada, Jrm. Kokai Tokkvo Koho,

JP 04314736 (Chem. Abst., 1993, 118, 234737~). 195. H. Suzuki, S. Katayama and F. Okada, JDn. Kokai Tokkvo Koho,

JP 04134737 (Chem. Abst., 1993, 118, 234738d). 196. H. Suzuki, S. Katayama and F. Okada, J m . Kokai Tokkvo Koho,

JP 04314738 (Chem. Abst., 1993, 118, 234739e). 197. M. Pomerantz, G. Krishnan, M.W. Victor, C. Wei and K.

Rajeshwar, Chem. Mater., 1993, 5, 705. 198. H.-P. Baldus, W. Schnick, J. Lucke, U. Wannagat and G.

Bogedain, Chem. Mater., 1993, 5, 845. 199. W. Schnick and V. Schultz-Coulon, Aanew. Chem.. Int. Ed.

200. H.R. Allcock, S.R. Puchner, M.L. Turner and R.J. Fitzpatrick, Macromolecules, 1992, 25, 5573.

201. V.A. Gubanov, G.A. Ivanov, A.I. Ponomarev and M.P. Grinblat, Kanch. R ezina, 1991, 25 (Chem. Abst., 1992, 117, 70630~).

202. W.D. Klobucar and D.M. Indyke, US 5101002 (Chem. Abst., 1992, 117, 9587~).

B: Chem. Sci., 1993, 48, 730.

33, 2335.

Enul. 1993, 32, 280.

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6: Phosphazenes 317

203.

204.

205.

206.

207.

208.

209.

210.

211.

212.

213.

214.

215.

216.

217.

218. 219. 220.

221.

222.

223.

224.

225.

226.

227.

S.G. Fedorov, G.S. Gol'din, G.S. Nikitina, N.L. Sin'k?, S.V.

1991, 64, 1963 (Chem. Abst., 1993, u, 1257232). E. Montoneri, P. Savarino, G. Viscardi, M.C. Gallazzi, M. Gleria and F. Minto, J. Inors. Oraanomet. Polvm., 1992, 2, 421. J.H.L. Crommen, J. Vandorpe and E.H. Schacht, Makromol. Chem., 1992, m, 1261. E. Schacht and J. Crommen, US 5104947 (Ghem. Abst., 1992, 117, 8741~). M. Gleria, F. Minto, M. Scoponi, F. Pradella and V. Carassiti, Chem. Mater., 1992, 4, 1027. H.R. Allcock, R.J. Fitzpatrick, K. Vissher and L. Salvati, Chem. Mater., 1992, 4 775. P. Cafelin, H. Hrudkova and V. Janout, V. I. Kalchenko and B. Valter, collect. Czech . Chem. commun., 1992, 57, 472. H.R. Allcock, K.B. Visscher and I. Manners, Chem. Mater.,

H.R. Allcock, S.R. Pucher, R.J. Fitzpatrick and K. Rashid, Biomaterials, 1992, 13, 857. J.H.L. Crommen, E.H. Schact and E.H.G. Mense, Biomaterials, 1992, u, 511. J.H.L. Crommen, E.H. Schact and E.H.G. Mense, Biomaterials, 1992, JJ, 601. J.H. Goedemoed, K. De Groot, A.M.E. Claessen and R.J. Scheper, J. Controlled Release, 1991, 17, 235. P. Caliceti, F.M. Veronese, 0. Schiavon, F. Marsilio, M. Carenza and S. Lora, proc. Int. SDD. Controlled Release Bioact. Mater.. 19th, 1992, J. Kopecek, Ed., 194 (Chem. Abst. , 1993, JJ&, 154319~). M. Kajiwara, ADD^. Biochem. Biotechnol., 1992, 33, 43 (Chem, Abst. , 1992, 117, 86245~). P. Caliceti, F.M. Veronese, F. Marsilio, S. Lora, R. Seraglia and P. Traldi, Ors. Mass SDectrom., 1992, 27, 1199. L.L. Fewell and L. Finney, Polvm. Commun., 1991, 12, 393. D. Briggs and G. Beamson, -1 . Chem,, 1993, 65, 1517. M. Gleria, F. Minto, L. Flamingni and P. Bortolus, J. Inors. Oraanomet. Polvm., 1992, 2, 329. F. Minto, M. Gleria, M. Scoponi, F. Pradella and P. Bortolus, J. Inora. Oraanomet. Polvm., 1992, 2, 405. E.I. Ryumstev, I.N. Shtennikova, D.R. Tur, G.F. Kolbina, E.V. Korneeva and V.G. Kulichikhin, Eur. Polvm. J., 1992, 28, 1031. E.I. Ryumstev, I.P. Kolomiets, I.N. Shtennikova, G.F. Kolbina, D.R. Tur and V.G. Kulichikhin, Vvsokomol. Soedin., Ser. A,, 1992, 24, 134 (Chem. Abst., 1992, 117, 192732~). M. Andrei, J.M.G. Cowie and P. Prosperi, aectrochim. Acta, 1992, 37, 1545. J.M.G. Cowie, A.T. Anderson, M. Andrei, A.C.S. Martin and C. Roberts, Electrochim. Acta, 1992, 37, 1539. J.M.G. Cowie, Makr omol. Chem., Macromol. S ~ D . , 1992, 53, 43. M. Kojima and J.H. Magill, Makromol. Chem., 1992, 2-23, 2731.

Sin'ko, V.N. Nosova and V.B. Zinov'eva, Jh. Prikl. Khim . I

1992, 4, 1188.

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

318

228.

229.

230.

231.

232.

233.

234.

235.

236.

237. 238.

239.

240.

241.

242.

243.

244.

245.

246.

247.

248.

249.

250.

251.

0 rganop h osp h or us Chemistry

S.V. Meille, A.R. Poletti, M.G. Gallazzi, M. Gleria and S. Bruckner, Polvmer, 1992, 33, 2364. E.M. Antipov, V.G. Kulichikhin and N.A. Plate, Polvm. Enq. Sci., 1992, 32 1188. V.S. Papkov, M.N. Il'ina, V.P. Zhukov, D.Ya. Tsvankin and D.R. Tur, Macromolecules, 1992, 25, 2033. D.Ya Tsvankin, M.V. Gerasimov, V.P. Zhukov, 1.I.i Dubovik, D.R. Tur and V.S. Papkov, J. Polvm. Sci.. Part B: Polvm. Phvs., 1992, 30, 851. A. Kuzemnieks, V.M. Parfeev, D.R. Tur and E.V. Smurova, Mekh. KomDoz. Mater. (Zinatne), 1992, 453 (Chem. Abst., 1993, 118, 192582r). A.V. Semakov, G.Ya. Kantor, E.K. Borisenkova, B.S. Khodyrev, D.R. Tur and V.G. Kulichikin, Vvsokomol. Soedin.. Ser. B., 1992, 34, 39 (Chem. Abst., 1992, 117, 152013d). S.G. Young, M. Kojima, J.H. Magill and F.T. Lin, Polvmer, 1992, 33, 3215. M. Kojima, S.G. Young and J.H. Magill, Polvmer, 1992, 33 4538. M.A. Gomez, C. Marco, I. Campoy, J.G. Fatou, T. Bowmer and R.C. Haddon, Mem.-Simp. Latinoam. Polim. 3rd., 1992, 101 (Chem. Abst., 1993, 118, 125357h). H.R. Allcock and K.B. Visscher, Chem. Mater., 1992, 4, 1182. C.J.T. Landry, W.T. Ferrar, D.M. Teegarden and B.K. Coltrain, Macromolecules, 1993, 26, 35. C.J.T. Landry, W.T. Ferrar and D.M. Teegarden, Eur. Pat. ADD^., EP 485033 (Chem. Abst., 1992, 117, 192999m). H.R. Allcock, C.J. Nelson, W.D. Coggio, I. Manners, W.J. Koros, D.R.B. Walker and L.A. Pessan Macromolecules, 1993, 2 6 , 1493. M.C. Gallazzi, E. Montoneri, P. Savarino, F. Bianchi and L. DiLandro, J. Mater. Sci. Lett., 1993, 12, 436. R. Soria, C. Defalque and J. Gillot, US 5066398 (Chem. Abst., 1992, 117, 9400~). E . S . Peterson, M.L. Stone, R.R. McCaffrey and D.G. Cummings, SeD. Sci. Technol., 1993, 28, 423. E.S. Peterson, M.L. Stone, R.R. McCaffrey and D.G. Cummings, SeD. Sci. Technol., 1993, 28, 271. E. Drioli, S.M. Zhang, A. Basile, G. Golemme, S.N. Gaeta and H.C. Zhang Gas SeD. Purif., 1991, 5, 252. E. Drioli, G. Golemme, A. Basile and S.M. Zhang, Kev Encr. Mater. 1991, 61-62, 611 (Chem. Abst., 1992, 117, 9575h). M.L. Stone, E . S . Peterson, M.D. Herd, D.G. Cummings and R.R. McCaffrey in, "Eff. Ing. Membr. Processes: Benefits Oppor. Proc. Int. Conf., 2nd." M.K. Turner (Ed.), Elsevier, London, 1991, 321. (Chem. Abst., 1993, 118, 7986q). J. Bravo, M.P. Tarazona and E. Saiz, Macromolecules, 1992, 25, 5625. M.P. Tarazona, J. Bravo and E. Saiz, Polvm. Bull.fBerlin1, 1992, 29, 469. J. Bravo, M.P. Tarazona and E. Saiz, Polvmer, 1992, 33, 3312. D.C. Lee, Pollimo, 1992, 16, 351 (Chem. Abst., 1992, 117, 49539f).

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online

6 : Ph osp h a z en es 319

252. L.K. Golova, G.Ya. Rudinskaya, S.A. Kupisov, D . E . Borodina, N.V. Vasil'eva, A.T. Kalashnik, D . R . Tur, S.P. Papkov, Vvsokomol. Soedin. Ser. A., 1992, 34, 135 (Chem. Abst., 117, 213498q).

253. Y. Yamamoto, M. Tanmachi and N. Takahata, JDn. Kokai Tokkvo Koho, JP 04154852 (Chem. Abst., 1992, 117, 173135k.

254. Y. Yamamoto, A. Hori and N. Takahata, JDn. Kokai Tokkvo Koho, JP 04154851 (Chem. Abst., 1992, 117, 173488~).

255. K. Higshimoto, K. Nakai, K. Hironaka, T. Hayakawa, A. Konaki and T. Nakanaga, JDn. Kokai Tokkvo Koho, JP 04167373 fchem. Abst., 1992, 117, 154605~).

256. K. Taeyama and T. Tonomura, JDn. Kokai Tokkvo Koho, JP 04277468 (Chem. Abst., 1993, 118, 172578r).

257. R. Shishikura and M. Takeuchi, JDn. Kokai Tokkvo Koho, JP 04253771 (Chem. Abst., 1993, 118, 1705992).

258. T. Nakanaga, A. Inubushi, Y. Tada, T. Kameshima, M. Taniguchi, T. Hatakawa and A. Komaki, JRn. Kokai Tokkvo Koho, JP 04008735 (Chem. Abst. , 1992, 117, 11446k).

259. H. Shinohara and N. Sakuta, Jan. Kokai Tokkvo Koho, JP 04145143 fChem. Abst., 1993, 118, 23216~).

260. T. Nakanaga, A. Inubushi and Y. Tada, JDn. Kokai Tokkvo Koho, JP 03231229 (Chem. Abst., 1992, 117, 161063~).

261. M. Ogawa, S. Noya and N. Eda, JDn. Kokai Tokkvo Koho, JP 05047421 (Chem. Abst., 1993, 118, 237736n).

262. M.P. Grinblat, A.M. Lundstrom, V.A. Gubanov and G.A. Ivanova, Kauch. Rezina, 1991, 8 (Chem. Abst., 1992, 117, 235572m).

104615a).

and N . A . Plate, SU 1680730 fchem. Abst., 1992, 117, 70940q).

263. Eur. Pat. ADD^., EP 511441 (Chem. Abst., 1993, 118,

264. E.K. Borisenkova, V.G. Kulichikhin, D.R. Tur, I.A. Litvinov

265. E.P. Hubin and G. Rousseau, Eur. Pat. ADD^., EP 490731 (Chem. Abst., 1992, 117, 133061b).

266. C . H . Kolich and S.C. Chang, US 5102963 (Chem. Abst., 1992, 117, 49478k).

267. G. Goins and H.M. Li, US 5105001 (Chem. Abst., 1992, 117, 61662~).

118, 256512~).

1993, 118, 118952~).

and R. Langer, PCT Int. ADD^., WO 9205778 IChem. Abst., 1992, 117, 14442s).

Khodael, M.I. Rios and K. Woolstencroft, Acta Crvstalloar., Sect. B: Struct. Sci., 1992, M I 683.

268. A.P. Mikhalkin, SU 1003645 (Chem. Abst., 1992, 117, 3958333). 269. H. Morika, Kobunshi Kako, 1992, 41, 297 (Chem. Abst., 1993,

270. M. Maki, JDn. Kokai Tokkvo Koho, JP 04352964 (Chem. Abst.,

271. S. Cohen, C. Bano, K.B. Visscher, M.B. Chow, H.R. Allcock

272. D. Bethell, M.P. Brown, M.M. Harding, C.A. Herbert, M.M.

Dow

nloa

ded

by Y

ale

Uni

vers

ity o

n 05

Mar

ch 2

013

Publ

ishe

d on

31

Oct

ober

200

7 on

http

://pu

bs.r

sc.o

rg |

doi:1

0.10

39/9

7818

4755

4451

-002

74

View Online