Phosphazenes

BY C. W. ALLEN

1 Introduction This chapter covers the literature of phosph(v)azenes. The

general pattern of development in this area is similar to that observed in the previous year's review with additional interest being shown in acyclic phosphazenes and characterization of solid- state behavior of polyphosphazenes. Reviews are limited to highly focused accounts which will be quoted in the appropriate sections below. 2 Acyclic Phosphazenes

Acyclic phosphazenes of the general formula R3P=NR' are refer- red to variously as phosphazo derivatives, phosphine imines and phosphoranimines. These terms will be used interchangably in this section. Selected aspects of the use of phosphazenes as ligands in coordination compounds has been reviewed.' An nmr study (I5N, 31P) of a series Ph3P=NC H R shows that 'JpN exhibits a linear corre- lation with aR or uR resonance effects at the nitrogen center.2 Exciting new chemistry has been found to arise from photolysis of di(isopropy1amino)phos- phorus (111) a ~ i d e ~ - ~ which yields the first monomeric phosphazyne, [ (C3H7) 2N] 2P=N. 3' Insertion into the phosphorus-nitrogen bond of the phosphazyne by dipolar reagents, XY, leads to [(C3H7)2N12P(X)= NY (XY = Me2NH,Me3SiC1 ,MegSiN3 ,PhN3 ,PhNCO) . phosphoryl azide gement of the intermediate phosphazene to give oxoiminophosphor- a n e ~ . ~ The Staudinger reaction continues to be used to generate monomeric phosphazenes. An interesting development in this area is the ozonolysis of the resulting triphenyl on tri-n-butyl phosphine imines as a new route to organic nitro compounds.6 of the Staudinger reaction to chlorophosphenium cations produces iminophosphonium species. Thus, the reaction of (R2NPC1) 'AlCl; (R=Me, Pr') with phenyl azide provides [R2NP (C1) =NPhl+A1C14- while the corresponding reaction with trimethylsilyl azide leads to the bis phosphocation, [R2NPN=P (C1) NR2 I '+.

6+4 thus indicating JpN provides a measure of

Photolysis of the [ (C3H,) 2N] 2P (0)N3 involves a Curtis-type rearran-

The extension

The reaction of

373

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

374 Organophosphorus Chemistry

(C13CMe2C0)2PN3 with phenyl azide yields the easily hydrolysed

phosphine imide azide (C13CCMe20)2P(N3)=NPh and the reaction of

C13CCMe20P(0)C1N3 with triphenylphosphine provides the expected product, C13CCMe20P ( 0 ) N=PPh3. Poly (vinylbenzyl triphenylphos-

phine imine) which is prepared from poly(vinylbenzy1 azide) and tri- phenylphosphine undergoes typical reactions with bases, aldehydes

and isocyanates . lo

phosphazo derivatives (1; R=H, MeO, NO2) by reaction with the ap- propriate organoazide . Azidocarboxylic acids, amides and amines

react with phosphorus(II1)compounds to give phosphine imines which

will undergo cyclization to spirophosphoranes if the functional 12 group of the azide has a mobile or highly nucleophilic proton.

The use of nitroaryl azides allows for the study of the phospha- 13 zines(2), which are intermediates in the Staudinger reaction.

These materials are destabilized by acids or bases.13 The basicity of a series of phosphazines (2; X=Me0,H,C1,Br,CF3N02, R=Ph) has been found to correlate with the 31P chemical shifts with the phos-

phorus nuclei being more shielded than in the corresponding phos-

n' phine imine. l4 - n=0-2, X=Br, NO2) and their decay to the phosphine imine-have been measured. The reaction of diazo 1,3-dicarbonyl derivatives

[RC(0)l2CN2 phosphazines. The preparation of 3-acyl, g-sulfonyl and _N-phos- phinyl triphenylphosphazo derivatives, RN=PPh3, is conveniently

accomplished by the reactions of triphenylphosphine with the appro- priate amide RNH2 (R = R'C(0) , R'S02, Ph2P(0)) in the presence of azodicarboxylates.

Tetramethyldioxaphosphanes are converted to the

The kinetics of formation of (2;R= (EtO) 3-n (morph)

with PR; (R'=OMe, NMe2) is also a route to isolable

17

A wide variety of other methods, including the oxidation of two-

coordinate phosphorus compounds, for the preparation of acyclic phosphazenes have been explored. The phosph(II1)azene RP=NR'

(R=2,2,6,6-tetramethylpiperidine, R'=SiMe3) undergoes oxidative

addition reactions to give the phosph(v)azenes ( 3 ; X=NMe2, Y=H;

X=MeO, Y=H; X=CC13, Y=Br; X=Y=Br; X=Y=Cl; X=NMe2, Y=Cl; X=Me3C0,

Y=C1) . l8 The phosphazene (3) derived from methanol is in equil- ibrium with the phosphite arising from a phosphorus-to-nitrogen proton transfer and the reaction with bromotrichloromethane also

gives the dibromophosphazene (3 ; X=Y=Br) . l8 Diimidophosphazenes ( 4 ; R=R'=SiMe3; R=SiMe3, R'=CMe3) can also be prepared from phosph-

(1II)azenes either directly by reaction with trimethylsilyl azide or in a subsequent elimination of Me3SiX from a phosphazene

(3;X=C1, Y=NCMe3 (SiMe3) ; X=Br, Y=N(SiMe3) 2)?8 Oxidation of

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphazenes 375

( 1 )

( 3 )

Me$ i CR R ' I

M e3Si N= PR " @ i=NSiMe3 CI I

( 5 ) ( 6 )

HCRR' I

I C I

( 7 1

Me,SiN = PR "

(11 1

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

376 Organophosphorus Chemistry

RP=NR' (R=mesityl, R'=CMe,) with ozone, Sulfur or selenium gives

phosph (v) azenes ( 4 ; X=O, S: Se) . l9 The reaction of RP=C (SiMe3) (R=mesityl)with trimethylsilyl azide gives the phosphazene (5; X=

C(SiMe ) ) .20 A sequence of bromine oxidative additions to (Me Si)Z

NP=CHSiMe3 followed by reductive elimination of Me3SiBr gives the novel tribromophosphoranimine Me3SiN=PBr2CHBrSiMe3. 21 The reac-

tion of mono (disilylamino) phosphines (Me3Si) 2NP ( R " ) CHRR' with

carbon tetrachloride leadsto g-silylphosphoranimines (6) via the elimination of chloroform. Reactions with phosphines containing

simple alkyl groups are more complex in that either chloroform or 22

Me3SiCC13 may be eliminated leading to (6) or (7) respectively. The reaction of tetraphenylimidothiophosphinate [Ph2P(S)I2NH with

C1CH2R leads to the monophosphazenes Ph2 (RCH2S) P=NP (S ) Ph2. 23 24

The combination of arylidinecyanoacetamides and p-tolyltetrachloro- phosphorane C (CN) =CHR. 25

chloride system with acid amides may be used to prepare the tri- ethoxyphosphazenes (EtO) 3P=NR. 2 6 t 27

phazenes. Three-coordinate phosphazenes of the type RR'NP(S)=NR react with (Ph3P) 2PtC2H4 to form complexes with side-on coordina-

tion of the thiophosphonyl function ( 8 ) . 28

combined with (Me Si) *NP (=NSiMe gives complexes with one (9) or two (10) phosphazene ligands. " The sequential addition of KSCN, R'NH2 and MC12 (M=Cu,Ni,Co,Zn,Sn) to hexachlorocyclodiphosphazenes, (RNPC1 leads to complexes with phosphazene-metal a-bonds

(11). 3a '' The reactions of the phosphorimidic triamide (Me2N) 3- P=NH

substitution of (Me2NI3P=N- for chloride and the formation of phos-

phonium compounds. The species [(Me2N)3P=N13P is a very strong base which easily accepts HC1 to give the phosphonium ion.

Acyclic dimerization of (Me2NI2P(Br)=NPh leading to the mixed phosphonium/phosphazene derivative [ (Me2N) 2P (Br) NPhP "Me2) =NPhl 'Br-

has been noted.

3 Cyclophosphazenes

appeared. The use of cyclophosphazenes as models for polyphos- p h a ~ e n e s ~ ~ and in the formation of inclusion ad duct^^^ has been discussed. Reviews in Russian and Polish cover cyclophosphazenes as lubricating materials36 and new reactions of cycloph~sphazenes~~

respectively.

3 2 3

provides phosphazenes of the type p-MeC6H4PC12=NC(0)- The reaction of the triethylphosphite/carbon tetra-

Some interest has been shown in the reactions of acyclic phos-

Diphenylzinc when

3

with the series PC13-n(NMe 1 (g=0-2), leads to both simple - 2 n

32

33

Little in the way of reviews of cyclophosphazene chemistry has

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphazenes 377

Calculations at the CND0/2 level indicate that the most favor- able conformation of spirophosphazenes is a chair spiro fragment on a planar phosphazene ring except when strong intermolecular

hydrogen bonding exists. 38

(ppheny1enedioxy)cyclophosphazene and its 1,2-dichloroethane clathrate along with the pphenylenedithio analog show a random

surface structure with identifiable impurities. The low C1

binding in the 1,2-dichloroethane clathrate reflects the higE pop-

ulation of donor atoms in the host.39

in N3P3C14Ph2 and N P C1 (NMe ) temperature dependence examir12d2~~ The effect of pressure on the 35Cl nqr spectra of N3P3C16 and the

been studied and intermolecular effects at high pressures have

been proposed at high temperatures. 41 of a series of aryloxyphosphazenes, N3P3(0Ar16, and anilinophos-

phazenes, N3P3(NHAr)6, show that in the aryloxy derivatives 70% of the ion current is carried by the P+ and [P+-ArO’l ions.42

fragmentation patterns observed for a series of alkylhydridophospha- zenes, 2,2’-N P C1 ( H ) R , show the importance of the (by now famil-

iar) McLafferty rearrangement. The preparation halophosphazenes is limited to a patent44

ESCA studies of aryl-substituted tris-

2P

The 35Cl nqr frequencies

have been assigned and their 3 3 4

and g forms of N4P4Clg has

The E. I. mass spectrometry

The

43 3 3 4

for

catalysis in the thermal tranformation of (NPCl2I3 to (NPC12)4-7 and the preparation of a mixture of non-geminal isomers of N4P4- F8,n_Xn_ (n=2,4; X=Cl,Br) by the reaction of the parent dimethyl- amino derivative with the appropriate hydrohalides .45

ization of di (isopropylamino) phosphazyne, (PriN) 2PzN,

2 ) leads to the first stable cyclodiphosphazene, [ (PriN) 2P=N] 2,

which exhibits a planar structure with long phosphorus-nitrogen

bonds.4 Photolysis of the phosphazyne also produces the first

hydridopentaaminocyclotriphosphazene, N3P3 (NPri) 5H. Detailed studies of the rates of dimethylaminolysis of N3P3X6(X=C1,F) in acetonitrile have been reported. 46 The formation of N3P3C16--

“Me2), (2=1-3) follows a bimolecular pathway but ,an evaluation of the activation energy data suggests the importance of a concerted

SN2(P) with synchronous addition of dimethylamine and departure of the chloride i o n .

SN2(P) pathway but is twenty times slower than the corresponding

chloride reaction. The dimethylaminolysis of N3P3C13(NMe ) and of N3P3C1 (0Ph) The tetrakis species

obtained from either the bis(dimethylamino1 or bis(ethy1amino)

The dimer-

(cf. Section

The formation of N3P3F5NMe2 also follows an

346 proceeds by a dissociative, sN1 (PI , pathway. 2,6,4,8-N4P4C14(NHEt)4(NMe2)4, which is

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

378 Organophosphorus Chemistry

derivatives,has been shown to be the precursor to the bicylic phos-

phazene N4P4C12 "Me2) (NHEt) (NEt)R (R=lo,2* amines) .47 The reac-

tions of N3P3Cl6 with (3-aminopropyl)methylsilanes give rise to

organosilicon phosphazene derivatives of the type N3P3C15NHCH2CH2R

where R=linear and cyclosiloxanes. 48

con tetrafluoride and alkylamino cyclotri- and cyclotetraphospha-

zenes has been examined with both five-and six-coordinate adducts

being observed. In most cases only endocyclic nitrogen coordination occursI with exocyclic nitrogen coordination occurring with spiro- cyclic ethylenediamino derivatives. 49

with a wide range of primary and secondary amines has been report-

ed. 50 The triphenylphosphazo moiety is strongly geminal-directing for secondary amines while primary amines follow the same pathway

that they do in reactions of N3P3C16.50 Aziridinolysis of 2,2-N3- P3C14 (NH2) under high dilution conditions gives N3P3 (NC H ) ( N )

while conventional conditions give both the expected product and

N3P3 (NC2H4) 5NH2. 51 Conversion of N3P3C14 (NIT2) to the bis triphe-

nylphosphazo derivative, 2,2-N3P3Cl4(N=PPh3I2, is accomplished by the use of the carbon tetrachloride/ triphenylphosphine system. 52 Dimethylaminolysis reactions leading to N3P3C14-Q(NMe2),(N=PPh3)2

(2=1-4) follow a geminal pathway suggestive of an SN1(P) process. The fully substituted derivative, N3P3(NMe2)4(N=PPh3)2, is isolated as the mono- or dihydrochloride with variable temperature nmr spec-

troscopy showing proton exchange between endocyclic nitrogen atoms.

The hydrolysis of the mono and bisamido chlorocyclotriphosphazenes N3P3C16-"(NH2) "(g=l , 2 ) leading to [ (NH) (PO2) 3 l 3- has been examined and an intermediate, N P3(OH)5NH21 is observed in the case of the monoamido derivative. 5'3.he first geminal to non-geminal isomeriza-

tion in cyclophosphazene chemistry is reported to occur in the for- mation of trans-2 , 4-N3P3 (OPri) d (NH2)

Thus, care should be exercised in using alkoxide derivatization as a means of structure proof.

Adduct formation between sili-

The reactions of N3P?l5N=PPh3

2 4 4 3 2

52

from the geminal diamide. 54

Interest in the products of reactions of polyfunctionalreagents

with cyclophosphazenes continues. The aziridinolysis of the spiro-

cyclic N3P3C14 [NH (CH2) , 4NH] derivatives leads to N3P3 ( NC H ) [NH- 2 4 4 (CH2) , 4NH] which exhibit significant anticancer activity. 55 A re- investigation of the reactions of diaminopropane and diaminobutane with N3P3C16 in non-polar solvents has led to the isolation of the

diSPir01 N3P3C12 "H (CH2) 14NHl , and the trispiro, N3P3 [NH ( C H ~ ) ~ , ~ - NH13, derivati~es.~~ spermine-bridged dimer (12) with l13-diaminopropane gives the mono,

Reactions at the zPClZ centers in the

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Ph osph azenes 379

di, tri and tetra spiro derivatives,while the addition of spermine with N3P3C16,2n[NH (CH2) 3NHl (n=l , 2) also leads to spermine-bridged dimers.57 The-reaction of the ansa (2,4-bridging) phosphazene (13) with diaminopropane leads to the spiro-ansa material (14), which in turn leads to a bridged dimer byreaction of theremainingphosphorus- chlorine bond with diamino-hexane. 58 The reaction of 1 I 3-dihydroxy- propane with N3P3C16 provides the first example dispiro/spiro-ansa isomerism in that two materials (15,161 having the composition N3P3C12 [O (CH2) 301 are obtained. 59 The spiro fluorocyclophospha- zenes N3P3F4 [NH (CH2) 3, 4NH] can be prepared from the diamines and N P F or by reaction of the corresponding chloro derivatives with potassium fluoride in acetonitrile. The fluorination of chloro pre- cursors was used to prepare a broad range of spiro fluorocyclotri- phosphazenes, N3P3F4 (XRY) (X=NMe, Y=O, R=(CH2) 2; X,Y=NH, R=(CH2) 3 ;

X,Y=O, R=(CH ) ) and N3P3F2(XRY12 (X=NMe, Y=O, R=(CH2l2; X,Y=NH,

R=(CH2) 3 ) .

Increased interest is being shown in the reaction of oxygen bases with cyclophosphazenes. The reaction of sodium p-chlorophenox- ide with N3P3C16 provides the series N3P3C16-n(OC6H4Cl)a. reaction follows a predominantly non-geminal path with traces of the geminal products being observed. A c&/trans ratio of 57:38 is observed at the bis stage of substitution.61 reaction with sodium phenoxide has been reinvestigated giving re- sults similar to the p-chlorophenoxide.61'62 aryloxy derivatives, N3P3C150C6H4R (R=H, p-Me3C, p-Br), has prepared.63r64 An improved synthesis of [NP (QC6H4NO2) 2 1 and the observation of two crystalline forms of this material have been reported.65 siloxane cleavage to give phosphazenes with one or two w-chloro- siloxane side chains. (OSiMe2)4C1 and 2,2-N3P3C14[(OSiMe2)4]2,have been prepared by the reactions of C1SiMe2(0SiMe2)3C1 with N3P3Cl50C4Hg and 2,2 -N3P3C14- (ONa) respectively. 66 Allyloxy and mixed allyloxy/trif luoroethoxy derivatives of N3P3C16 have been prepared.67 fluoroalcohols RfOH (Rf=CH2(CF2)2,4,6H) with N3P3C16 in the presence of water and pyridine in nitrobenzene gives rise to oxobridged dimers (17) which can undergo further reactions with fluoroalkax- ides, phenoxide, alkoxides and amines. 68 The (vinyloxy) f luorocyclo- triphosphazenes N3P3F6-1?(0CH=CH 1 (2=1-5) have been prepared from

2 n the reactions of the enolate anion of acetaldehyde with N3P3F6. This reaction follows an exclusively non-

n

3 3 6

602

The

The corresponding

A series of mono- been

The interaction of N3P3C16 and (OSiMe2)3 leads to

Model compounds in this series, N3P3C15-

The reactions of

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

380 Organophosphorus Chemistry

geminal pathway.69 presence of large cations in acetonitrile gives N3P3C16-n_ (o-M+) (g=1,2) with two isomeric non-geminal derivatives being obtained when n=2. 70 Tris (2-phenylenedioxy) cyclotriphosphazene inclusion

adducts with various organic solvents have been examined by the

use of deuterium nmr giving information on guest conformation, dynamics and intrachannel orientation. '' iation of acrylic monomers in this clathrate givespolymers with enhanced stereoregularity and no radiation cross-linking . 7 2 The preparation and clathrate formation of t r i s (pmethoxy-2-phenylene-

dioxy) cyclotriphosphazene has been reported. 73 The reaction of sodium thiolates with N5P5Cl10 provides the series

(n=1-4; R=Et,Ph), which have been shown by 31P nmr spectroscopy to consist exclusively of geminal isomers. 74 (3,4-toluene-dithiolato)cyclotriphosphazene has been reported.

The controlled hydrolysis o f N3P3C16 in the

n

Gamma ray (60Co) irrad-

N P C1 5 5 10-pR)g

The preparation of tris 73

The study of reactions at the exocyclic position of cyclophos- phazenes has largely focused on the chemistry of aminophenoxycyclo- triphosphazenes,which are prepared by the reduction of the corre- sponding nitrophenoxy derivative. The reaction of maleic or phthalic anhydride with the aminophenoxy center gives a maleamic acid which on sequential thermolysis goes on to the maleimide and the poly(ma1eimide). This strategy has been applied to N3P3(NH-

C6H5) (OC6H4NH2) 4 , 7 5 N3P3 (OPh) (OC6H4NH2) and N3P3 (OC6H4NH2) 6. 77 The last compound can also be converted to the amide by reaction

with acetic anhydride. 6 5 obtained from the Friedel-Crafts reaction of N3P3(OC6H4X)6 (X=H,Me) and polychloroalkanes. Soluble prepolymers are obtained when care

ful stoichiometric control is used.

Cross-linked, cyclomatrix polymers are

7 8

The synthesis of phosphazenes with phosphorus-carbon bonds and

the reactions of organometallic reagents with cyclophosphazenes continues to be an active area of investigation. Thermally in- duced halogen scrambling of 2,2 -N3P3C14PhBr produces the non-gem- inal N P C1 Br Ph and N3P3C12Br3Ph derivative^.^' study of the reactions of alkyl Grignard reagents with dimethyl- amino-chlorocyclotriphosphazenes has been made. *O

reaction with 2,4,6-N3P3Cl3(NMe2I3 in ether followed by treatment with triethylamine produces N3P3R3 (Me2) and N3P3R2 (0C2H5) We2)

(R=Me,Et). reagent yields N3P3(0Et)3(NMe2)3 while in THF the Grignard reac- tion leads to N3P3Me [O(CH2) 4C1] (NMe2)3 with hydrogen chloride gives N3P3C13R3.

A detailed 3 3 3 2

The Grignard

The same reaction using MgBr2 in place of the Grignard

(NMe2) 3 . The reaction of N3P3R3- The Grignard

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphazenes 38 1

CI

(16 1

I II CI,P, ,PCIz

'N

(17)

I II CIZP, ,PCIZ

'N

(20 )

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

3 82 Organophosphorus Chemistry

reaction of 2,4,6,6-N P C1 (NMe2I4 gives N3P3R2(NMe2l4,which can

be deaminated in two steps to give N3P3C13R2 (NMe2) and N3P3Cl4R2.*O

The reaction of N3P3C16 with alkyllithium followed by quenchingwith isopropyl alcohol has been examined with both alkylated, N P C1 R, N - P3C14R2, and hydridioisopropoxy, N P C1 (13) OCHMe;!, derivatives have

been observed.81 The reaction of methyllithium with N4P4C18 leads to bi(cyc1otetraphosphazenes) when quenched with methyl iodide (18;R=Me) or ethyl iodide (18;R=Et) while quenching with isopropanol gives the

hydridophosphazenes N4P4C16 (H) Me and N4P4C16 (H)OCHMe2 :2 The reac- tions of N P F with lithioacetylenes has been studied. In addition

to the previously reported 2, 2-N3P3F4 (CrCPhI2 traces of the non- geminal derivatives were observed. The reactions with lithiotri-

methylsilylacetylene produces the monosubstituted derivative and, at the bis stage of substitution, comparable amounts of geminal and non-geminal N P F (CECSiMe3)2. The fluoride ion-induced desilylation

of the trimethylsilylacetylene fluorophosphazenes in ethanol pro-

duced the terminal acetylenes with concomitant ethoxy substitution,

N3P3F4-n (CrCH) (OEt) N P F R (R=NMei, n-C4Hg, t-C H ) yields the gerninal derivatives

2,2 -N3P3F4 (Ph) R.84 The discovery of new and exciting phosphazene

derivatives containing transition-metal organometallic fragments 5 continues. 3 3 6

C H ) yields, when M=Cr, N P C1 CrCp(CO)3,while when M=W, Mo ametal- halogen exchange occurs leading to 2,2 -N P C1 (Cp)MCp(C0)3. The

intermediate ion in the metal-halogen exchange can be trapped with methyl iodide to yield 2, 2-N3P3C14 (Me) WCp (Co) 3. 85 The reaction of N P C1 with Na Fe (C0l8 leads to the complex phosphazene-iron car-

bony1 derivatives N3P3C14Fe2 (CO) (19; M=M'=Fe(C0)4 1 and N P C1 - Fe3 (CO)lo (20 ; M=Fe) . 86 The reactions of N3P3C14Fe2 (CO) other organornetallic reagents allows for preparation of a wide

variety of metallophosphazenes. with Fe (CO) or Fe2 (CO) leads to N3P3C14Fe3 (CO) while the reac- tion with Ru3(CO) 12 produces N P C1 Fe R U ( C O ) ~ ~ (20; M=Ru) .86

CpCo (CO) M=Fe (CO) obtained. Fe (CO) 4CoCp ( C O ) yields N3P3C14 [RhCp (CO) 1 2. Fe2(C0)8 with C O ~ ( C O ) ~ leads to a mixed cobalt/

87 iron carbonyl cluster (21).

3 3 2

3 3 5 3 3 3 4

3 3 6

3 3 4

(n=l ,2) .83 The Friedel-Crafts phenylation of

3 3 5 4 9

The reaction of N P C1 with MCp(C0); (M=Cr,W,Mo; Cp=q - 5 5 3 3 5

3 3 4

3 3 6 2 2

3 3 4 with

The reaction of N3P3C14Fe2(C0)8

If 3 3 4 2 is the organometallic reagent, N3P3C14Fe (CO) 4CoCp (CO) (19;

(19; M=M'=CoCp (CO) ) are with N3P3C14Fe2 (C0l8 or N3P3C14-

The reaction of N3P3C14-

, M'=CoCp (CO)) and N3P3C14 [CoCp (CO) I The reaction of RhCp (CO)

As in previous years, there is an extensive applications

literature dealing with the preparation and uses of cyclophospha-

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphazenes 383

zenes.

and cyclotetraphosphazenes is of interest as is the acaridical activity of monoaminopentachlorocyclotriDhosphazenes . 91 The pre- paration of phosphazenes coupled to carboxylic acidsg2 and the pre

paration of condensed alkoxyphosphazenesg3~ 9 4 has been noted.

largest body of patent literature involves the use of cyclophos- phazenes to impart fire resistance to naturally occurring (ligning6, Chitosang7) and synthetic materialsg5 such as fibers?? 9 5

101 f ilmsa8 insulating sheets"

Heat-resistant properties of cyclophosphazenes are also of interest in adhesivesIo2' lo3 and elastomeric polymers. lo4 of adhesives is improved by using phosphazene additive^:'^-^'^ as is the antiwear characteristics of transmission oil.

4 CvcloPhosDha (thial zenes

The anticancer activity of various aziridino c y c l ~ t r i - ~ ~ t89

The

resins6" loo and epoxy oligoesters.

The shelf-life

109

As is usually the case in phospha(thia)zenes with two-or three-

coordinate sulfur atoms, reactions occur in the thiazene portion of the molecule. Oxidative addition reactions of 'the two struc- tural isomers 1 5- (Ph2PNI2(SN) ( 2 2 ) and 1,3- (Ph2PN) (SN) (23) have

been studied.'"

( 2 2 ) leads to the formation of sulfur-halogen bonds in (Ph2PNI2- (SNX) (24) . The equivalent reactions of the 1,3-isomer (23) result in ring contraction to give (Ph2PN) SNCl (25; X=C1) or ring ex-

pansion to give the [ (Ph2PN)4(SN)212+ ion (26). The corresponding neutral compound (271, which can be prepared by the reaction of

(Ph2PN)2NSC1 with triphenylantimony, reacts with iodine or bromine

to yield (Ph2PN) 2SNI or (Ph2PN) (NS) 'Br;. Cycloaddition of norbor-

nadiene occurs with 1,3- but not 1,5- (Ph2PN) reaction of tetrasulfur tetranitride, S4N4, with diphenylchloro-

phosphine also leads to the six-membered ring species, (Ph2PN)2- SNC1. Continued reaction with excess phosphine results in ring-

opening degradation to give the linear phosphazane [Ph2P(C1)=NP- (C1) Ph2 I 'Cl-. Analogous reactions of S4N4 with phenyldichloro-

phosphine or phosphorus trich1ori.de lead to less-well character-

ized P2SN3 rings. The reaction of (Ph2PNI2 NSCl with KI,Ph2Hg,

Me3SiNMe2, Et2NH or C H

The addition of Br2 or S02C12 to the 1,5-isomer

2 (NS) 2. The

NHleadsto the sulfur-bonded derivatives 5 10 (Ph2PN) 2NSX (25; X=I,Ph,NMe2,NEt2, NC5Hlo) . Treatment of (Ph2PN)

NSCl with bromine or iodine leads to the cationic species (Ph2PN) 2SN+. The bromo derivative (Ph2PN) 2SNBr can be prepared from [ (Ph2PN) 2NSl+Br; either by thermolysis or by treatment with triphenylantimony. The halides (Ph2PNI2SNX (X=Cl,Br,I) are con- verted to the linear phosphazene [Ph2P (NH2) =NP (NH2) Ph2] + X- by

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

3 84 Organophosphorus Chemistry

hydrolysis.111

reported for the model compound (H2PN) (SN)' show that the P2SNf

ring is a six n-electron system with *-bonding localized in the

NSN and PNP segments and is weak for the PN bond connecting these segments.

tinue to be of interest. The controlled hydrolysis (NPC12)NSOC1

in acetonitrile occurs at the phosphorus atom(s) giving both the mono ( [NPC12 (NPC10) NSOClJ -1 and geminal disubstituted, monoproto- nated ( [NPC12 (NHP02) NSOCl] -) derivatives. 70

NPC12(NSOC1) lead to a stable, monosubstituted anion, [(NPC10)-

(NSOC1) 21-.76 Further hydrolysis of NPC12 (NSOCl) leading to [NP (OM) (NS (0) OM) 2 1 (M=NH4', Ag', K') has been reported. The reaction of NPC12(NSOPh)2 with alkyl-lithium reagents is similar to the corresponding reactions of N3P3C16 i>. it proceeds via metal-halogen exchange. Quenching the reaction with isopropanol leads to mono- and dialkylated materials along with a hydridoiso- propoxy derivative. 81

[NP (NC2H4) 2 ] 2NS0 (NC2H4) Patents covering modifications of the pentachloro precursor, (NP- C12)2NSOC1, have appeared.

SOAz reduces the membrane potential and the membrane potential dependent amino acid transport without being cytotoxic. 11'

addition of SOAz stabilizes the right-handed helix of DNA against conversion to the left-handed by carcinogenic nickel compounds. Studies in mice show that administration of SOAz induces a slight prolongation of anesthesia but other CNS, cardiovascular and res-

118 piratory systems are unchanged. 5 Miscellaneous Phosphazene-containing Ring Systems

& initio Hartree-Fock-Slater SCF calculations

112

Phospha(thia)zenes with four-coordinate sulfur atoms also con-

Similar reactions of

Due to its significant biological activity , (SOAz) is at the center of several studies.

In Streptococcus pneumoniae,

The

This section covers carbocyclic systems which have one or more phosphazene units as part of the ring system. CND0/2 calculations

show that the most favorable conditions for cyclization of C13P=NC (R2) =C (R1) CN to the diazaphosphorines ( 2 8 ) require a a-donor

(R1) in the 2-position. '19 phine (Me2SiCH2CH2SiMe2)NP(CMe3)CH2SiMe3 with carbon tetrachlor- ide leads to a novel phosphazene-containing ring system ( 2 9 ) ?2 The

The reaction of the silylaminophos-

reactions of Me2Pf.1C0 with diacetyl esters go via the intermediate formation of azaphospholines (30) . 12' 1,2-diketones to triazaphospholes leads to phosphazenes (31) which are in a dimerization equilibrium.121 phazenes oligomers with benzil also leads to phosphazenes ( 3 2 ) . 12'

The oxidative addition of

The reaction of A3-phos-

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosp hazenes 385

(22) (231

I X

( 2 5 )

(27 )

Me,

(29)

*2

(24)

(26)

N b C L C R’ I II ‘N

CL,P\ ,CR2

(281

R’OC

( 3 0 )

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

386 Organophosphorus Chemistry

Patents covering the preparation of l - p h o ~ p h a - 2 ~ 4 ~ 5 - t r i a z e n e s ~ ~ ~

and the use of perfluoroalkyl phospha-s-triazenes as lubricating flu ids with an tioxidant and anticorrosion characteristic s1

appeared.

6 Polyphosphazenes

have

This section is devoted to polymers containing open-chain phos-

phazenes. Polymeric systems containing cyclophosphazene units are covered in Section 3 . Polyphosphazenes are discussed in two gen- eral introductions to inorganic macromolecules. 34' 124 Reviews of

polyphosphazenes as thermally stable elastomers125 and of organo-

metallic derivatives126 have appeared. Reviews concerning poly-

phosphazene chemistry127 and their f lame-retardant properties128 are available in Korean and Russian respectively.

(NPC12)n, continue.

the ionization chamber of a mass spectrometer has been studied and the mechanism found to be identical to that proposed for bulk poly- merization. While the reaction of N3P3C16 and (OSiMe2) at

250° gives cyclophosphazenes with siloxane side-chains (cf.Section 31, the only high-polymeric material observed is (NPC12)n. 66 The catalytic effect of tetra~henyl-tin'~' or molybdenum and tungsten silicates'31 on N3P3C16 polymerization has been noted. If linear

chlorophosphazenes are heated with ammonium chloride the molecular weight increases. 132

C13P=NP (S) C12 to C12P (S) [NPCl I C1 has appeared.

2,2 -N3P3C14PhBr. the trif luoroethoxy, phenoxy and piperidino derivatives. 79

polymers of the monophenyl halocyclotriphosphazenes with N3P3C16 and of N3P3C15Ph with N3P3C15Me were prepared. 79 Homopolymers of

the transannular bridged fluorophosphazenes N3P3F4(Cp2Ml2 ( 3 3 ;

M=Fe,Ru) have been prepared and converted to the trifluoroethoxy

derivatives. Mixed iron/ruthenium copolymers were also reported. The unbridged,monosubstituted organometallic derivative N3P3F5-

C5H4RuCp has also been converted to the homopolymer but the iron

analog will not undergo polymerization without the addition of a catalytic amount of N3P3Cl6. The copolymerization of N3P3C15- OC6H4R (R=H, CMe3, Br) with N3P3C16 has been reported.63 Patents

describing methods for removal of sodium salts resulting from the reaction of ("PC1 ) with sodium alkoxides or aryloxides are avail- able.135,136 '

Investigations of the synthesis of poly(dichlorophosphazene), The gas-phase polymerization of N3P3C16 in

A patent describing the thermolysis of 133

2 n Halogen scrambling was noted in the bulk polymerization of

The resulting homopolymers were converted to

Co-

The preparation of poly[bis(benzoyloxy)phospha-

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphazenes 387

zene] 137 and poly (catecholphosphazene) 138 have been reported. latter compound is of interest in view of the low stability of the analogous cyclophosphazene derivatives. The hydrophilic character of poly(organophosphazenes) can be enhanced by addition of malonic acid esters to the solution containing the nucleophile which is to be used for derivatization of (NPC12)n. 13' Variations of the ther- ma1 and hydrolytic stability of poly(fluoroa1koxyphosphazenes) pre-

methoxyethoxy)ethoxyphosphazene, [NP(OC2H40C2H40Me) ] (MEEP), has been prepared and found to form complexes with a wide variety of metal salts.

The

pared in THF or in THF/toluene have been noted. 14* Poly [ 2 (2-

2 ;

141

The MEEP-metal complexes mentioned above exhibit good room- temperature electrical conductivity and appear to be excellent candidates for thin-film electrodes. 14' have shown that poly [bis (E-tolylamino) phosphazene] and poly [bis- (2-naphthoxy)phosphazene] are insulators which become photoconduc- tors when doped with trinitrofluorenone(TNF) due to side-chain/TNF interactions. 142 Spectrophotometric and voltametric studies of the interaction of iodine and poly[bis(p-tolylamino)phosphazene] in methylene chloride suggest the occurrance of charge transfer between the halogen and side-chain nitrogen sites. 143 A variety of physical measurements have been applied in the study of the effect of low-dose W and y irradiation on poly[(trifluoroethoxy)- fluoroalkoxyphosphazene]. Initial increase in side-chain mobility due to side-chain cleavage is followed by decreased mobility due to cross-linking. 144 The use of poly [ (trif luoroethoxy) -f luoroal- koxyphosphazene] as an amorphous hydrophobic polymer showed that the initial effect of molecular motion on thrombogenesis is inde- pendent of morphological order and/or a'ssociated water. The publication of several papers dealing with the solid-state char- acterization, with emphasis on morphology and behavior at the mesophase transition, T(l), of poly[bis(trifluoroethoxy)phospha- zene] (PBFP) has occurred this year. The mesomorphic phase of PBFP co-exists with the crystalline and amorphous phases. The crystalline-to-mesomorphic transition occurs at x(1) but a spher- ulitic superstructure presists. On cooling a more stable rod-like morphology is observed. 146

the properties of PBFP depending on sample history including a hysteres's in x(1) .147 (spherulitic) and melt-crystallized (needle aggregates) samples of PBFP . 147

Conductivity measurements

There are noticeable differences in

The morphology varies between cast films

A detailed study of cast and annealed films has un-

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

388 Organophosphorus Chemis fry

covered several polymorphic forms in addition to the meso-

phase. 148r149 On heating, PBFP progresses from a chain-folded form

through T ( 1 ) to a two-dimensional chain-extended form. After pass-

ing to the melt at 2, and recooling, the two-dimensional form is observed followed by a three-dimensional modification. 14* 14'

Solution-grown single crystals of PBFP and poly[bis(2,4-dichloro- phenoxy)phosphazenel have been obtained and exhibit the chain-fol-

ded structure with polymorphic forms occuring in the phenoxy com-

pound. place. 15' phosphazene) ,15* and the ability of PMF O-rings to withstand fuel leaks' 5 3 have been measured.

on f lame-resistant, poly (propoxyph0sphazene)-treated Rayon have been obtained.

Below Tm crystal thickening occurs as chain extension takes The water-vapor transmission rate of poly( f luoroalkoxy-

Performance and toxicological data

154

A variety of applications of polyphosphazenes continue to be

explored. These include use as gas-permselective membranes, 155r fire proofing of polymeric materials157 including PVC cable insul-

ati01-1;~~ heat-resistant coatings159 pnd primers for polyurethane

sealants. 160 A method for producing tetrahalogen alkoxyphospha-

zenes is available. 16' cations such as heparinized poly(organophosphazenes) as blood con-

tacting devices, localized release of anesthetics bound to PO 1 ypho sphaz ene s

zenes lFj being developed.

7 Molecular Structures of Phosphazenes

fraction except for one (noted) case using electron diffraction.

All distances are in picometers.

It is gratifying to see biomedical appli-

and dental se a1 an t s containing po lyphospha-

The following structures have been determined by &-ray dif-

Compound Comments Re f e renc e s

(t-C H ) P=NH PN 165.2(ll),electron diffraction 165 4 9 3

( 3 4 )

( 3 5 )

P=N 153.9; PN endocyclic 166.3, 166.9, 166 exocyclic 162.0

{(C3H7)2P=N12 P N endocyclic 164.4(9)-165.1(8). Planar ring

(36) Mean PN endocyclic 159.0, N3P3 essentially planar

167

168

trans-2,4-N P PN endocyclic 156-160, preliminary data 54 3 3- (oC3H7) 4 (m2) 2

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphazenes 389

(33)

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

390

( 1 5 )

( 1 6 )

N3P3C14 [O(CH2) 201

N3P3C14[0(CH2) 3ol

N3P 3C l4 0 ( CH2 1 4O I

2 , 2 -N3P3F4 (Ph) CMe3

( 3 7 )

N3P3C15CrCp (CO)

2,2 -N3P3Cl4(Cp)M0Cp(CO),

( 1 9 ; M=M'=Fe(CO)&)

( 20 ; M=Fe)

( 2 0 ; M=Ru)

( 2 1 )

(19;M=M'=CoCp(CO))

( 1 9 ; M=M'=RhCp(CO))

( 2 4 ; X=Br)

Organ oph osph orus Chemistry

Comments R e f e r e n c e s

PN e n d o c y c l i c 157.1(4)-161.1(2); N3P3 p l a n a r ; NC2H4 pyramidal PN e n d o c y c l i c 159 .4(3) -160 .5(7) , 159.2 (5)-161.6 (6) . Two independent m o l e c u l e s . S t r o n g H-bonding between NH a n d H 2 0

PN smaller a t s p i r o P t h a n PC12. P r e l i m i n a r y Communication

f. PNP=112.7O a t N w i t h i n a s b r i d g e . P r e l i m i n a r y communication

PN 158.1(2) , 1 5 6 . 2 ( 2 ) , 157 .1(2) ; LOP0 9 8 . 3 ( 2 ) " , L P O C 111.2(1)"

PN 1 5 8 . 2 ( 4 ) , 1 5 6 . 1 ( 4 ) , 157 .5(2) ; LOP0 105.4(3)" , LPOC 117.6(4) '

PN 1 5 9 . 2 ( 2 ) , 1 5 6 . 1 ( 2 ) , 157.5(2); L OPO 106.1 (1>",L POC 121.9 (2)"

PN 161.8(1) , 1 5 2 . 7 ( 2 ) , 156.5(1); N P p l a n a r w i t h i n 0.7 pm

PN 160.8(3) , 156 .2(3) , 157 .2(3) ; P-P same as i n p h e n y l d e r i v a t i v e

N3P3 non-planar a t PCr by 27 pm

3 3

PN 161-153;

PN 154-165; N3P3 non-p lanar a t PMo by 16 pm

PN 163,154,159;LFePFe 76 .2" ; N P p l a n a r

3 3

PN 166, 156-160; N P d e v i a t e s from p l a n a r i t y 3 3

PN 166, 157-162; N P d e v i a t e s f rom p l a n a r i t y 3 3

PN 167.1, 162.5, 153-160; N P d e v i a t e s from p l a n a r i t y 3 3

PN 154.3(6) -163 .9(8) ; N P d e v i a t e s from p l a n a r i t y 3 3

PN 156.3 (5) -164.3 (4); N P d e v i a t e s f rom p l a n a r i t y 3 3

PN 153(1)-163(1); N P d e v i a t e s f rom p l a n a r i t y 3 3

55

56

59

59

169

169

169

84

170

8 5

85

8 6

8 6

8 6

87

87

8 7

87

PN 1 6 1 . 3 ( 6 ) , 162.9(6); 110,171 S a toms d i s p l a c e d f rom p l a n e o f r i n g ; S-Br t r a n s c o n f i g u r a t i o n

No S-S bond PN 158,166. 110

PN 158,162. S-S bond

110

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosp hazenes 391

Compound

( 2 5 ; X=Cl)

( 2 5 ; X=I)

(25; X=NMe2)

( 2 5 ; X=Ph)

1

2

3

4

5

6

7 8

9

i0 11

12 13

14

15

16

17

18

19

20 21 22

23

24

Comments Referencas

PN 158.0(4) , 166.7(5) ; 112 S atom o u t of P2N3 p lane

PN 158.6(4) , 166.2(9) ; S atom o u t of P2N3 p lane

112

PN 159.4(2) , 160.6(2) 112

PN 159.6(3) , 161.8(3); P SN r i n g p l ana r

2 3

112

Disorder of O(in NSO) and NC2H4 (on S ) ; two d i f f e r e n t conformations

172

Ln 2" based on o r i e n t a t i o n of NC2H4 groups

References

O . J . Scherer , Nachr. Chem., Tech. Lab., 1984, 32, 582 (Chem. Abst., 1984, - 101, 110975h). M. Pomerantz, B.T. Ziemnicka, Z.M. Merchant, W.N. Chou, W.B. P e r k i n s and S. B i t t n e r , J . Org. Chem., 1985, 50, 1757. S. S i ca rd , A . Baceiredo, G . Bertrand and J.P. Majoral , Angew. Chem.,Int. - Ed. Engl., 1984, 23, 459. A . Baceiredo, G . Bertrand, J .P. Majoral , G. S i ca rd , J . Jaund and J. Galy, J . Am. Chem. SOC., 1984, 106, 6088. A . Baceiredo, G . Bertrand, J .P . Majoral , F.El-Anba and G. Manuel, J . Am. Chem. SOC., 1985, 107, 3945. E . J . Corey, B. Samuelsson and F.A. Luzzio, J . Am. Chem. S O ~ . , 1984, 106, 3682. M.R. Marre, M. Sanchez and R. Wolf, J. Chem. Soc., Chem. Commun., 1984, 566. N . I . Gusar ' , M.P. Chaus, A . N . Chernega, M. Yu. Antipin, I . E . Boldeskul, Yu. G. Gololobov, J . Gen. Chem. USSR , 1984, 54, 1137. I.Yu. Budilova, N . I . Gusar' and Yu. G . Gololobov, J . Gen. Chem. USSR , 1984, 54, 1771. H.L. Cohen, J. Polym. Sci.,Polym. Chem. Ed., 1983, 23, 1661. V.P. Kukhar, T.N. Kashova, L.F. Kasukhin, M.P. Ponomarchuk, J . Gen. Chem. USSR , 1984, 54, 1360. Yu. G. Gololobov, N . I . Gusar' and M.P. Chaus, Tetrahedron, 1985, 41, 793. P.P. Onys'ko, N.V. P rok l ina , V.P. Prokopenko and Yu. G. Gololobov, J . Gen. Chem. USSR , 1984, 54, 289. V.P. Prokopsnko, N.V. P r o k l i n a and P.P. Onys'ko, J . Gen. Chem. USSR, 1984, - 54, 721. B.A. Arbuzov, A.M. Polozov and N.A. Polezhaeva, J. Gen. Chcm. USSR , 1984, - 54, 1755. M.P. Ponomarchuk, L.F. Kasukhin, M.V. Shevchenko, L.S. Sologulo and V.P. Kukhar, J. Gen. Chem. USSR , 1985, 54, 2204. S. B i t t n e r , Y . Assaf , P. K r i e f , M. Pomerantz, B.T. Ziemnicka and C.G. Smith,

--

-

--

J . Org. Chem., 1985, 50, 1712. V.D. Romanenko, A.V. Ruban, S.V. Iksanova and L.N. Markovskii, J . Gen. Chem. USSR , 1984, 54, 278. L.N. Markovskii, V.D. Romanenko, A.V. Ruban and A.B. Drapai lo , J. Chem. Soc., Chem. Commun., 1984, 1092. Z.M. Xie, P . Wisian-Neilson and R.H. Nei lson, Qrganometa l l i c s , 1985, 2, 339. R.R. Ford, R.H. Nei lson and R. Thoma, Inorg. Chem., 1985, 24, 1993. R.R. Ford, M.A. Goodman, R.H. Nei lson, A.K. Roy, U.G. Urszula and P. Wisian-

-

--

Neilson, Inorg. Chem., 1984, 23, 2063. N.G. Zabirov, E.L. Gol 'dfarb, R.A. Cherkasov and A.N. Pudovik, J. Gen. Chem. USSR , 1 9 8 4 , 3 , 2502. N.G. Zabirov, E.L. Gol 'dfarb, F.G. Zabirov and R.A. Cherkasov, USSR P., SU 1,122,667 (Chem. Abst., 1985, 102, 166950 ) .

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

392 Organophosphorus Chemistry

25

26

27

28

29

30

31

32

33

34 35

M. El-Deek, M.A. Hassan and S . El-Hamshary, Pak. J . Sc i . Ind. Res., 1983, 26,59 (Chem. Abst., 1984, =,7278j). J. Steinbach, E. Herrmann and L. Riese l , Z . Anorg. Al lg . Chem., 1984, 511, 51. J . Steinbach, E . Herrmann, L . Riese l , Ger. (East) P . , DD 208156 (Chem. Abst., 1984,101, 211461t). O. J . Scherer , H . Jungmann, C . KrUger and G . WolmerschXuser, Chem. Ber., 1984, 117, 2382. V.D. Romanenko, V.F. Shul’gin, V.V. Skopenko and L.N. Markovskii, J . Gen. Chem. USSR , 1984, 54, 2501. A.E. A r i f i e n and E.H.M. Ebrahim, Pol . J. Chem., 1984, 2, 41 (Chem. Abst., 1985, 102, 185178e). A.E. Ar i f ien , Pak. J. S c i . Ind. Res., 1984, 27, 127 (Chem. Abst., 1985, - 102, 71606n). P.P. Manchenko, G.N. Koidau, A.M. Pinchuk and A.V. Kursanov, J . Gen. Chem. USSR , 1984, 54, 1581. A.P. Marchenko, V.V. Miroshnichenko and A.M. Pinchuk, J . Gen. Chem. USSR , 1984, 54, 1086. H.R. Allcock, Chem. Eng. News, 1985, 63(11), 22 . H.R. Allcock, 1984, Inc lus ion Compd., Vol. 1, 351. Ed. J.L. Atwood, J .E.D. Davies and D.D. MacNicol, Academic, London.

- --

_ _ _ -

36 A.M. Danilov, L.S. Nesternova and T.M. Salamova, Neftepererab. Neftekhim.,

37 R. Kotek, Wiad. Chem., 1983, 37, 749 (Chem. Abst., 1984, 101, 191985m). 38 R. Lahana, F. Crasnier and J.F. Labarre, Inorg. Chim. Acta, 1984, 90, L65. 39 D.T. Clark, H.S. Munro, P. Finocchiaro, E. L i b e r t i n i and A . Recca, J. Chem.

40 K.R. Sr idharan, J . Ramakrishna, K . Ramachandran and S.S. Krishnamurthy,

41 V. Krishnan, K.R. Sr idharan and J . Ramakrishna, Polyhedron, 1985, k, 739. 42 A. B a l l i s t r e r i , S . F o t i , S. Lona and G . Pezzin, Org. Mass Spectrom., 1985,

20, 165. 43 KJ. Harr i s , R.D. Minard and H.R. Allcock, Org. Mass Spectrom., 1985, 20,

321. 44 M. Poetzsch, G . I . Mitropol’skaya and V.V. Kireev, USSR P.,SU 1,141,069

(Chem. Abst., 1985, 102, 1691883. 45 T.T. Bamgboye, Polyhedron, 1985, 4 , 657. 46 K.V. K a t t i and S . S . Krishnamurthy; J. Chem. SOC., Dalton Trans., 1985, 285. 47 P.Y. Narayanaswamy, K.S. Dhthathreyan and S.S. Krishnamurthy, Inorg. Chem.,

1985, 24, 642. 48 V.M. Kireev, V.A. Kovyazin, V.M. Kopylov, M.G. Zai tseva and G . I . Mitropol l -

skaya, J . Gen. Chem. USSR, 1984, 54, 1692. 49 B.S. Suresch, V. Chandrasekhar and D.K. Padma, J. Chem. S O C . , Dalton Trans.,

1984, 1787.

1984, 5, 19 (Chem. Abst., 1984, 101, 2135542).

Research (2). 1984, 230.

Polyhedron, 1984, 2, 867.

50

51 52

53

54

55

56

57 58

S.S. Krishnamurthy, R . Ramabrahman, A.R. Vasudeva Murthy, R.A. Shaw and M. Woods, Z . Anorg. Allg. Chem., 1985, 522, 226. A. Mahmoun, P. Castera and J .F. Labarre , Inorg. Chim. Acta, 1984, 86, L41. C. Lensink, B. de Rui te r and J . C . van de Grampel, J. Chem. SOC. , Dalton Trans., 1984, 1521. M. Kouri l , L. Meznik and K. Dostal , Col lec t . Czech. Chem. Commun., 1984, - 49, 392. J . K . Fincham, M.B. Hursthouse, H.G. Parkes, L.S. Shaw and R.A. Shaw, J. Chem. SOC., Chem. Commun., 1985, 252. J.F. Labarre, G . Guerch, F. Sournies , F. Spreaf ico and S. F i l ippeschi , J. Mol. S t r u c t . , 1984, 117, 59. N. E l Murr, R. Lahana, J.F. Labarre and J .P. Declercq, J. Mol. Struc t . , 1984, 117, 73. F. Sournies, R. Lahana and J.F. Labarre, Inorg. Chim. Acta, 1985, 101, 31. F. Sournies , J .F . Labarre, P.J . H a r r i s and K . B . Williams, Inorg. Chim. Acta, 1984, 90, L61.

--

--___

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphuzenes 393

59

60

61

62 63

64

65 66 67

68

69 70

7 1 72 73

74 75

76 7 7 78

79 80 81 82

83

84

85

86

87

88 89

90

91

92

93

94

95

S .R . Contractor , M.B. Hursthouse, H.G. Parkes, L.S. Shaw, R.A. Shaw and H . Yilmaz, J . Chem. SOC. , Chem. Comun., 1984, 675. K.C.K. Kumara and S.S. Krishnamurthy, Indian J . Chem., Sect . A, 1984, =, 717. S . Karthikeyan and S . S . Krishnamurthy, Z . Anorg. Allg. Chem., 1984, 513, 231. S.A. A l i , E . Herrmann and B. Thomas, Z. Chem., 1984, 24, 133. V.V. Kireev, M. Poctzsch and G . I . Mitrolpol ' skaya, Deposited DOC., V I N I T I , 1983, 5089 (Chem. Abst., 1985, 102, 79398s). P . Michael, V.V. Korshak, V.V. Kireev and G . I . Mitropol'skaya, USSR P.,SU 1,113,382 (Chem. Abst., 1985, 1 0 2 , 6 8 2 5 ~ ) . J. Bornstein, D.P. Macatone and P.R. Berquis t , Inorg. Chem., 1985, 24, 625. H.R. Allcock, D . J . Brennan and R.W. Allen, Macromolecules, 1985, 18, 139. J. Brossas and G . Clouet, Fr . Demande FR 2539746 (Chem. Abst., 1985, 102, 7285e). S.G. Fedorov, G.S. Gol'din, E.V. Kotova, A.V. Kis in and V.M. Nosova, J. Gen. Chem. USSR, 1984, 54, 673. C.W. Al len and R.P. Bright , Inorg. Chim. Acta, 1985, 99, 107. B. DeRuiter, H . Winter, T . Wil t ing, J . C . van de Grampel, J . Chem. SOC., Dalton Trans., 1984, 1027. E . Meirovitch and I . Belsky, J . Phys. Chem., 1984, 88, 4308. H.R. Allcock and M. Levin, Macromolecules, 1985, 18, 1324. P. Finocchiaro, E . L i b e r t i n i and A. Recca, J. Chem. SOC., Perkin Trans. 1 , 1984, 1735. B. Thomas and G . Grossman, Z. Anorg. Allg. Chem., 1985, 523, 112. D. Kumar, G.M. Fohlen and J . A . Parker , J. Polym. S c i . , Polym. Chem. Ed., 1984, 22 , 1141.

---

______

D . KumG, J . Polym. Sc i . , Polym. Chem. Ed., 1985, 23, 1661. D. Kumar, J . Polym. Sci . , Polym. Chem. Ed., 1984, 22, 3439. K.V. Katt i and S.S. Krishnamurthy, J. Polym. Sc i . , Polym. Chem. Ed., 1984, 22. 3115. - H.R. Allcock and M.S. Connolly, Macromolecules, 1985, 18, 1330. H.R. Allcock, J .L. Desorcie and L . J . Wagner, Inorg. Chem., 1985, 24, 333. H. Winter and J . C . van de Grampel, J. Chem. SOC., Chem. Commun., 1984, 489. H. Winter and J . C . van de Grampel, Recl. Trav. Chim. Pays-Bas, 1984, 103, 241. C.W. Al len, J.L. Desorcie and K . Ramachandran, J. Chem. SOC., Dalton Trans., 1984, 2843. C.W. Al len, S. Bedel l , W.T. Pennington and A.W. Cordes, Inorg. Chem., 1985, - 24, 1653. H.R. Allcock, G.H. Riding and R.R. Whi t t le , J . Am. Chem. Soc., 1984, 106, 5561. H.R. Allcock, P.R. Suszko, L . J . Wagner, R.R. Whit t le and B. BOSCO, J. Am. Chem. SOC. , 1984, 106, 4966. H.R. Allcock, P.R. Suszko, L . J . Wagner, R.R. Whi t t le and B. BOSCO, Organo- m e t a l l i c s , 1985, 4, 446. R i j k s u n i v e r s i t e i t Groningen, Neth. P., NL 8,300,573. J.F. Labarre, G . Guerch, G . Levy and F, Sournies , Fr.Demande FR2,536,751 (Chem. Abst., 1984, 101, 2307705). J . C . van de Grampel and A.A. van der Huizen, PCT I n t . Appl. WO 8414523 (Chem. Abst., 1985, 102, 204102~) . C. Milhar t and Z . Simon, Bul-St i int . Teh. I n s t . P o l i t c h "Train Vuia" T i m i - soara , Ser . Chim., 1983, 28, 97 (Chem. Abst., 1984, lOJ, 171356d). H.R. Allcock, T.X. Neenan and W.C. Kossa, US P.4,440,921 (Chem. Abst., 1984, - 101, 7830h). Otsuka Chemical Co. Ltd.,Jpn. Kokai Tokkyo Koho JP 60/20931 (Chem. Abst., 1985, 102, 221631h). Otsuka Chemical Co. Ltd. ,Jpn. Kokai Tokkyo Koho JP 60118526 (Chem. Abst . , 1985, 102, 204507e) . Otsuka Chemical Co. Ltd., Jpn. Kokai Tokkyo Koho JP 60/20932 (Chem. Abst., 1985, I&, 221352t).

--

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

394 Organophosphorus Chemistry

96 H. Struszczyk and J.E. Laine, Pol . PL 125877 (Chem. Abst., 1984, 101, 212-

97 H . Struszczyk and G . G . A l l an , Po l . PI; 127084 (Chem, Abst . , 1985, 102, 98 Teikoku Chemical I n d u s t r y Co. L td . , Jpn. Kokai Tokkyo Koho JP 59/71329

99 Otsuka Chemical Co. L td . , Jpn. Kokai Tokkyo Koho J P 59/26987 (Chem. Abst.,

959y).

1 3 3 9 1 5 ~ ) .

(Chem. Abst . , 1984, 101, 91709f) .

1984, 101, 4 2 6 4 1 ~ ) . 100 D . K u m c G . Fohlen and J . A . Pa rke r , U.S. Pa ten t Appl. US 599126 (Chem.

Abst., 1985, 102, 167676m). 101 Chem. Abst . , 1985, 102, 1 6 7 8 5 5 ~ . 102 Chem. Abs t . , 1984, 101, 39443a. 103 Chem. Abst . , 1984, 101, 394422. 104 Yamanouchi Pharmaceut ical Co. Ltd.,Jpn.Kokai Tokkyo Koho JP 59/105028

105 N. Nagasawa and T . Nakata, U.S. P.US 4496685 (Chem. Abst . , 1985, 102,

106 Taoko Chemical Co. L td . , Jpn.Kokai Tokkyo Koho JP 59/157163 (Chem. Abst . ,

107 Chem. Abst . , 1984, 101, 8133v. 108 I n s t i t u t e f o r Product ion and Development Science, Jpn. Kokai Tokkyo Koho

109 R.G.Ya1yshev and V . T . Kostygov, U.S.S.R. P.SU 1143766 (Chem. Abst . , 1985,

110 T B u r f o r d , T. Chivers , M.N.S. Rao and J .F. Richardson, Ino rg . Chem., 1984,

111 T. Chivers and M.N.S. Rao, Inorg. Chem., 1984, 23, 3605. 112 N . Burford, T. Chivers , M. Hojo, W.G. Laidlaw, J .F . Richardson and M. Trsic,

Ino rg . Chem., 1985, 24, 709. 113 A . I . Rozanov, E.N. Beresnev, M.A. Kop'eva, V . I . Sokol and M.A. Porai-

Kosh i t s , Zh. Neorg. Khim., 1984, 29, 1687 (Chem. Abst., 1984, 101, 1 2 1 9 2 6 ~ ) . 114 Otsuka Chemical Co. L td . , Jpn. Kokai Tokkyo Koho JP 59/3013 (Chem. Abst . ,

1984, 101, 2114672). 115 Otsuka Chemical Co.

1984, 101, 154263d). 116 M.C. Trombe, C. Beaubestre , A.M. Sautereau, J . F . Labarre , G. Lanee l l e and

J.F. Tocanne, Biochem. Pharmacol., 1984, 33, 2749. 117 S. L i q u i e r , P. Bourtayre, L. P i z z o r n i , F. Sournies , J.F. Labarre and

E. T a i l l a n d i e r , Anticancer &, 1984, 4, 41. 118 J . Yamamoto, A. Kanda, H. Murakami, K . T a j i m a , K . Toide, A. Haruno, U. Yuj i ,

Inbush i g . , Oyo Yakuri, 1984, 27, 511 (Chem. Abst . , 1984, 101, 6952b). 119 I.E. Boldeskul, A.S. Tarasevich and V.P. Kukhar, J. Gen. Chem. USSR, 1984,

54, 1588. 120 E G . Yarkova, I . V . Konovalova, L.A. Burnaeva, N.M. Kashtanova, G.S. Khaf-

izova and A.N. Pudovik, J. Gen. Chem. USSR, 1984, 54, 1761. 121 0. D i a l l o , M.T. Boisdon, C. Malavaud, L. Lopez, M. Haddad and J. Barrans,

Tetrahedron L e t t . , 1984, 2, 5521. 122 Yu. G. T r i s h i n , A.S. Panevin, V.N. Ch i s tok le tov , V.A. Gal ishev and

A.A. Pe t rov , USSR P. SU 1,081,170 (Chem. Abst . , 1984, 101, 1 1 1 1 9 8 ~ ) . 123 K.J .L . Pac io rek , US P a t . Appl. US 601,873.

(Chem. Abst . , 1984, 101, 2 3 1 7 7 2 ~ ) .

133268q).

1985, 102, 1 5 0 5 4 6 ~ ) .

JP 59/18759 (Chem. Abs t . , 1984, 101, 3 9 6 7 0 ~ ) .

102, 2064242).

23, 1946.

Ltd.,Jpn.Kokai Tokkyo Koho JP 59/3014 (Chem. Abst.,

124 B.R. C u r r e l l , Chem. i n B r i t a i n , 1985, 21, 557. 125 R.A. Rhein, Report , NWC-TP-6372, SBI-AD-E900297 (Chem. Abst . , 1984, 101,

126 H.R. Allcock, P rep r . Am. Chem. SOC., Div. P e t . Chem., 1982, 27, 652 (Chem.

127 O.S. Kwon, Hwahak Kwa Kongop U i Chinbo, 1984, 24, 326 (Chem. Abst . , 1984,

74028r).

Abst., 1984, 101, 7 3 1 8 9 g ) T - ---

101. 5 5 5 4 0 k r - 128

129 M. Gleria, G. Audisio, S . D a o l i o F P . T r a l d i and E , Vecchi, Macromolecules,

D'yachkov, G.M. Dzhilkibaeva and M.F. Sal ikhova, T r . I n s t . Khim. Nauk, Akad. Nauk Kaz.SSR, 1983, 58, 168 (Chem. Abst. 1984, 101, 212034t).

1984, 17, 1230.

-----

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

9: Phosphazenes 395

130

131 132 133

134 135

136

137

138

139

140

14 1

142

143

144

145

146

147

148 149 150 15 1

152

153 154 155

156

157

158

159

160

16 1

162

163

G . I . Mitropol'skaya, M.V. Mi lashui l i , V .V. Kireev, V.V. Korshak and M.V. Denisova, U.S.S.R. P . SU 1113388 (Chem. Abst., 1985, 102, 25266d). M. Kajiwara, Angew. Makromol. Chem., 1985, 2, 71. M.H.Li, U.S. P. US 4447408 (Chem. Abst., 1984, 101, 241483). C . Abou and R. De Jaeger , Belg. P.BE 900090 (Chem. Abst., 1985, 102, 1326763). H.R. Allcock, K.D. Lavin and G. Riding, Macromolecules, 1985, 18, 1340. Teikoku Chemical Industry Co. Ltd . , Jpn. Kokai Tokkyo Koho JP 59/45324 (Chem. Abst., 1984, g, 81728). T.F. Longo, V.R. Sagar and M.L. Stayer , U.S. P.US 4477656 (Chem. Abst., 1985, 102, 4 7 1 7 3 ~ ) . L.G. Fomenko, A.A. Mirkuskin, V.V. Kireev, I . G . Karasina and Z.K. Zinovich, Deposited Doc. V I N I T I , 1983, 2340 (Chem. Abst., 1984, 101, 131248~) . L.G. Fomenko, S.K. Zinovich, V.V. Kireev and A.V. Kis in , Vysokomol. Soedin., Ser. B y 1984, 26, 416 (Chem. Abst., 1984 a, 1312441)). M.G. ? a k l a k o v , y . I . As t r ina , V.V. Kireev, E.M. Myasoedov and G.M. Ragin- skaya, U.S.S.R. P.SU 1085993 (Chem. Abst., 1984, 101, 5 6 0 0 0 ~ ) . I . A . Metkin, G.N. Nikiforova, V.V. Korol'ko and G.A. Ivanova, Kauch. Rezina, 1984, 5 (Chem. Abst., 1984, 101, 8457d). P.M. Blonsky, D.F. Shr iver , P. Austin and H.R. Allcock, J. Am. Chem. Soc., 1984, 106, 6854. P. DiMarco, G . Giro, S . Lona and M. Gler ia , Mol. Cryst . Liq. Cryst . , 1985, 118, 439. G. Eieggiato, G. Casalbone-Miceli and F. Mori, Eur. Polym. J., 1984, 20, 1183. W.M. Reicher, F.E. F i l i s k o and S.A. Barenberg, J. Col loid I n t e r f a c e 5, 1984, 101, 565. S.A. Barenberg, W.A. Reichert and K.A. Mauritz, Ann. N.Y. Acad. S c i . , 1983, - 416, 538 (Chem. Abst., 1984, 101, 60104a). T.P. Russe l l , D.P. Anderson, R.S. S t e i n , C.R. Desper, J.J. Beres and N.S. Schneider, Macromolecules, 1984, 17, 1795. T. Masuko, R. Simeone, J . H . Magil l and D . J . Plazek, Macromolecules, 1984, 1 7 , 2857. M. Kojima and J . H . Magil l , Polym. Commun., 1984, 25, 273. M. Kojima and J . H . Magil l , Makromol. Chem., 1985, 186, 649. M. Kojima, W. Kluge and J.H. Magil l , Macromolecules, 1984, 17, 1421. R.D. Helander and W.B. Tol ley, Natl. SAMFE Symp. Exhib., 1984, 29, 1373 (Chem. Abst., 1984,101, 24820~)- - G.W. Lawless , A.K. Behme, R.P. Mortimer, H.W. Pol ley , T.H., Elastomerics , 1984, 116, 22 (Chem. Abst., 1985, 102, 633946). C . J . F x o n o , Report, SAA.LC/MM-8149, 1983 (Chem. Abst., 1984, 101, 7 4 0 9 8 ~ ) . B.V. Het t ich , Text. R e s . J . , 1984, 54, 382. Asahi Glass Co. L t d x p ; Kokai T z k y o Koho J P 59/154105 (Chem. Abst., 1985, 102, 25961b). H. Imai, T . Kiyota, H. I t o h and K. Sakata, Fr . Demande FR 2542211 (Chem. Abst., 1985, 102, 966353). G.S . Gol'din. S.G. Fedorov, E.V. Kotova, S.F. Kravtsova, G.S. Niki t ina , V.A. Rusakov and L.M. Sukhova, Nov. 061. Primeneniya Metallorgan. Soedin., - M., 1983, 159 (Chem. Abst., 1984, 101, 8620b). V. DaROVa, M. Kolanova, M. Georgieva, Khim. Ind. (Sof ia ) , 1984, 56, 116 (Chem. Abst., 1984, 101, 172258k). Otsuka Chemical Co. 1984, 101, 74454b). I n s t i t u t e f o r Production and Development Science, Jpn.Kokai Tokkyo Koho JP

-

-

Ltd.,Jpn.Kokai Tokkyo Koho JP 59/36157 (Chem. Abst.,

58/172431 (Chem. Abst., 1984, 101, 8803~). Teikoku Chemical Indus t ry Co. Ltd.,Jpn.Kokai Tokkyo Koho JP 59/71330 (Chem. Abst., 1984, 101, 73296q). H.R. Allcock and T.X. Neenan, U.S. P US 4451647 (Chem. Abst., 1984, 101, 97663h). H.R. Allcock, P.E. Austin and T.X. Neenan, U.S. P US 4495174 (Chem. Abst., 1985, 102, 172651d).

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online

3 96 Organophosphorus Chemistry

164 165

166

167

168

169

170

171 172

Nihon U n i v e r s i t y , Belg. P. BE 899654 (Chem. Abs t . , 1985, 102, 32326b). D.W.H. Rankin, H. Robertson, R. Se ip , H. Schmidbaur and G . Blaschke, J. Chem. SOC.. Dal ton Trans. . 1985. 827. ______ M.R. Marre, M. Sanchez, R. Wolf, J. Jand and J . Galy, Can. J . Chem., 1984, 62. 2186. - A . N . Chernega, M. Yu. An t ip in , Yu. T. Struchkov, I . E . Boldeskul , M.P. Pono- marchuk, L.F. Kasukkin and V.P. Kukhar, J . Gen. Chem. USSR, 1984, 54, 1766. Yu. E. Ouchinnikov, V.E. Shklover , Yu. T . Struchkov, A.A. Remizova, V.M. Kopylov, V.A. Kovyazin and V . V . Kireev, Z . Anorg. A l lg . Chem., 1985, 523, 14. S.R. Cont rac to r , M.B. Hursthouse, L .S . Shaw, R . A . Shaw and H. Yilmaz, Acta C r y s t a l l o g r . , 1985, m, 122. R.R. Whittle, J . L . Deso rc i e and H.R. A l l cock , Acts C r y s t a l l o g r . , 1985, % 546. P.E. Marsh and K.M. S l a g l e , Ino rg . Chem., 1985, 24, 2114. J . Galy, R. E n j a l b e r t and J.F. Labarre , & C r y s t a l l o g r . , 1985, w, 116.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

05 M

arch

201

3Pu

blis

hed

on 3

1 O

ctob

er 2

007

on h

ttp://

pubs

.rsc

.org

| do

i:10.

1039

/978

1847

5543

76-0

0373

View Online