4 Phosphine Oxides and Related Compounds

1 Introduction ‘All quiet on the phosphine oxide front’ might describe this years’ literature. Once more, synthetic work continues to dominate the field, and advances have been made in general synthetic methods using phosphine oxide handles, and in the synthesis of phosphorus-containing analogues of natural products. Claims for the ‘first’ phosphiran oxide synthesis seem to be better founded than previously. High interest in phosphine oxide complexes and extractants for cations continues.

2 Preparation The phosphine oxide (1) is formed during recrystallization of the alkynyl- phosphines (3). This extraordinary hydration reaction is believed to proceed via a hydroxyphosphorane, as shown in Scheme 1, and to be a consequence of the use of wet ethanol as solvent. The oxide (2) is also formed when R is -GCPh.

Ph

Ar‘ I WetEtOH ~

R = H or C f C P h

OH

Ar = C,II,R-o

Ph (3)

/J Ph

(2) minor

Scheme 1

W Winter, Angew. Chem., Int. Ed. Engl,, 1978, 17, 947.

69

(1) major 5 4 4 8 %

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

70 Organophosphorus Chemistry

A wide range of phospholen l-oxides have been prepared by the diene- addition route outlined in Scheme 2.2 These reactions have been directed towards the synthesis of phospha-steroids, or their tricyclic precursors, and structures (4)-(7) are illustrative of this work.2

Reagents: i, MePC12; ii, H2O. Scheme 2

The phosphorinen l-oxides (8; R=Me or Ph) and the dienylphosphine oxide (9) are formed by ring opening of the vinylcyclopropane In the presence of water, the products are the phosphinoyl chlorides (11) and (12),3 and these may have been formed by the routes outlined in Scheme 3.

+

PPh c1 c1 c1 c1

3 C. Symmts and L. D. Quin, J. Org. Chem., 1979, 44, 1048. 8 Y. Kashman and A. Rudi, Tetrahedron Lett., 1979, 1077.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

Phosphine Oxides and Related Compounds 71

0 I 1 I

PhPCL,-AlCl, + H20 * PhPH + HC1 + AlCl,

Cl

fL+& c1 c1

c1 c1 c1 CI

Scheme 3

Alcoholysis of the di-ylide (13) gives the bisphosphine oxide (14).4 The oxides (1 5 ; R1 = Et or Ph) have been prepared in low yield by a somewhat harsh Arbusov reaction.

Ph2P(CI)=C=P(Cl)Ph2 IPJCH,

(15) R' = Ph 20% R' = Et 20%

The synthesis of various a-keto-phosphine oxides has been the subject of an unusually large number of papers over the yearY6-l1 and, almost inevitably, these also dwell on their high reactivity. Only the bis-oxide (16), prepared by oxidation, seems to be free of stability problems.6 For the simple acyl series, the oxides (17) dimerize readily,? while others (18) are more stable, and their chemistry has been studied in some detail.? The dimerization and rearrangement of the diphenylphosphine oxides (17; R= CF, or C7H15) have been described. *

R. Appel and K. Waid, Agnew. Chem., Int. Ed. Engl., 1979, 18, 169. V. S. Tsivunin, V. G. Zaripova, T. V. Zykova, and A. I. Razumov, J . Gen. Chem. USSR (Engl. Transl.), 1978, 47, 282. E. Lindner and G. Vordemaier, Z. Naturforsch., Teil B, 1978, 33, 1457. G. Frey, H. Lesiecki, E. Lindner, and G. Vordermaier, Chem. Ber., 1979,112, 763.

* E. Lindner and H. Lesiecki, G e m . Ber.. 1979, 112, 773.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

72 Organophosphorus Chemistry

0 0 0

II I1 -25°C [ph2i1c/cF3 R3-PCOR' II I PhzP-cR R = CF, (or C,H,,)

117) 'OCOCF, R2 (18) R' = Rz = R3 = Me

or R' = R2 = Me, R3 = Ph 01 R' = CF,, R2 = Me,

R3 = Ph

Others paper@-ll have been devoted to the nature of the interaction of mole- cular oxygen with various phosphines, and it is clear from these that the reactions are complex. A number of unexpected reactions, including P--C bond cleavage and oxygen insertion, are now known to compete with 'simple' oxidation, and the experimental conditions seem to control the balance between these processes : see Scheme 4 for a summary.

ref. 9 0 0

0 ll [ %p ] I1 II PhCPPh, -% PhC--I+'Ph, - PhCOPPh, -+ (PhCO),O + (Ph,PO),O

0 0 ll I I

PhC-PPh, -+ dimer

ref. 10 0

RPPh, + R-R + Ph,PPPh,

oxide dioxide Scheme 4 (part)

@ E. Lindner and G. Vordermaier, Chem. Ber., 1979,112, 1456. 10 H. Lesiecki, E. Lindner, and G. Vordermaier, Chem. Ber., 1979,112, 793. 11 W. Mahler, Inorg. Chem., 1979, 18, 352.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

Phosphine Oxides and Related Compounds ref. 11

0 0

(CFJ,P O': (F,C),PH + (F3CO)Q II II

73

oxidation of phosphines

Scheme 4 (cwtinued)

A number of purely preparative oxidations or sulphurations of phosphines have been described. The oxides (19),12 (20),13 (21),14 (22),15 and (23)lS have been prepared using hydrogen peroxide (also ozone 16), and the sulphides (24) l7

using sulphur.

0 0 II

(Me,CCHJ, PR, -n (21) n = 1 or 2

II But,P=O ( B U ~ CH,),PBU~

(20) (19)

(24) a; R' = H, Rz = PMe, S I I

b; R' = PMe,, Rz = H

The phosphole (25) has been converted into the phosphorin derivative (26) and the ester (27).lS

3 Reactions at Phosphorus Addition reactions of phosphorus compounds of general structure (28) have been reviewed and some reactions of secondary phosphine oxides (28; R1,R2 = alkyl

12 H. Schmidbaur and G. Blaschke, Z. Naturforsch., Teil B, 1978, 33, 1556. 1s H. Quast and M. Heuschmann, Angew. Chem., Int. Ed. Engl., 1978, 17, 867. 14 G. Singh and G. S. Reddy, J. Org. Chem., 1979, 44, 1057. 15 J. M. J. Tronchet, J.-R. Neeser, and E. J. Charollais, Helv. Chim. Ada, 1978, 61, 1842. 16 F. D. Yambushev, 2. I. Usmanov, R. R. Shagidullin, F. G. Khailitov, A. M. Galeev, and

17 L. D. Quin and L. B. Littlefield, J . Org. Chem., 1978, 43, 3508. I* F. Mathey, Tetrahedron Lett., 1979, 1753.

N. Kh. Tenisheva, J. Gen. Chem. USSR (Engl. Transl.) 1978, 48, 1612.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

74 Organophosphorus Chemistry

or aryl) inc1~ded.l~ Rearrangements of diphosphine monoxides (29) have been reviewed.20

0 0

Interest in conversions of phosphine oxides into phosphoranes continues. The phosphorane (30) and the phosphoranes (31) have been described in detailY2l and X-ray analysis of (31 ; R = Ph) reveals that it possesses an almost ideal tbp structure. Of particular interest is the stability of the hydroxyphosphorane (32),*l which is the closest known relative of the presumed intermediate in hydrolysis of phosphoryl ester derivatives. A Russian group has also described the phosphoranes (31),22 prepared by routes similar to those originally described by Granoth et aLa3 Trifluoromethanesulphonic anhydride (33) has been used to

0

(i) KMnO, (ii) H'

(31) R = alkyloraryl 0

1' A. N. Pudovik and I. V. Konovalova, Synthesis, 1979, 81. SO I. F. Lutsenko and V. L. FOSS, Vesm. Mosk. Uniu., Khim., 1978, 19, 379. 11 Y. Segall and I. Granoth, J. Am. Chem. SOC., 1978, 100, 5130. 21 K. A. Petrov, V. A. Chauzov, N. Yu. Mal'kevich, and S. M. Kostrova, J . Gen. Chem.

I* Y. Segall, I. Granoth, A. Kalir, and E. D. Bergmann, J. Chem. Soc., Chem. Commun., USSR (Engl. Transl.), 1978, 48, 74.

1975 399.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

Phosphine Oxides and Related Compounds 75

R

convert phosphine oxides into phosphoranes, under conditions that are mild and yet eff i~ient .~~

A novel phosphorus-extrusion reaction on the oxides (34) leads to the a-bipyridyls (35).25 When tetramethyldiphosphine disulphide (36) is desulphur- ized in the presence of a proton donor, dimethylphosphine is

s s 0 ll

3Me,PH + Me2POH 11 II Bu,P, H,OL 2MezP-PMe,

(36)

Re-examination of the reactions of arsine sulphides (37) with alkyl halides has revealed that the intermediate arsenite (38) can exchange groups, and hence lead to the 'problem' products, arsines (39) and their salts (40). 27 These reactions are outlined in Scheme 5. Reactions of di-n-alkylphosphine oxides (41) with halogenocarboxylic acids and esters have been reported.

R13As=S + R2X __L_ Rf2AsSR2 + R'X

(37) (3 8)

R:AsSR2 R:As + R1As(SR2), (39)

R',As + R'X --+ R1,As'X'

Scheme 5 (40)

4 Reactions of the Side-chain [3 + 2lCycloaddition reactions of phosphine oxides have been reviewed, and include those in which the oxide acts as a dipolarophile, e.g. (42) and (43), and

24 S. Antczak and S . Trippett, J. Chem. SOC., Perkin Trans. 1, 1978, 1326. z5 G. R. Newkome and I). C. Hager, J. Am. Chem. SOC., 1978,100, 5567. 2ci A. Trenkle and H. Vahrenkamp, Z. Natiirfursch., Ted B, 1979, 34, 642. a7 B. E. Abalonin, Yu. F. Gatilov, and G. I. Vasilenko, J. Gen. Chem. USSR (Engl. Trawl.),

28 S. Nakasato, H. Hirata, and K. Higuchi, Yakugaku, 1978, 27, 513. 1978,48, 370.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

76 Organophosphorus Chemistry

those in which the oxide acts as the dipolar species, e.g. (44).28 Improved condi- tions for the cyclization of bis-(1 -alkynyl)phosphine oxides (45) have been reported.30

0 II + -

0 0 0 < R2P-N=N=N II

R,P-C=C I 1 II

[R(CHJ ,+PH R2P-C=C-

(41) (42) I (44) (4 3)

0 ll NH,OAc

PhP(C=CR), in

(45)

- 80% An earlier clairn3l that the phosyhiran oxide (46) can be prepared by an

internal displacement has been re-in~estigated.~~ The product of the treatment of (47) with DBN has now been shown to be a vinylphosphinous salt (48),82 although (46) cannot be ruled out as an intermediate. In the meantime, con- vincing chemical and spectroscopic evidence for the ‘first’ phosphiran oxide has

0 0 \\ /ph I1

PhP(CHBrPh), * Ph Ph / \*

(4 7)

Ph -6 Ph

now been advanced for the tri-t-butyl derivative (49). lJ The preparation and some of the reactions of (49) are outlined in Scheme 6.

Wittig-Horner reactions (Scheme 7) of the oxides (50) illustrate their facility as equivalents of p-acyl anions, i.e. RCOCHzCH2-.33 The same paper includes descriptions of several approaches to ketone precursors of analogues of (50), some of which are presented in Scheme 8. Terpenoid polyenes may be synthe- sized using diphenyl(gerany1)phosphine oxide (51).s4 The reaction of (51) with citral is regio- and stereo-selective.

29 N. Khusainova and A. N. Pudovik, Russ. Chem. Rev. (Engl. Transl.), 1978, 47, 803.

3l E. W. KOOS, J. P. Vander Kool, E. E. Green, andJ. K. Stille, J. Chem. SOC., Chem. Commun.,

sz H. Quast and M. Heuschinann, J . Chem. SOC., Chem. Commun., 1979, 390. 38 A. Bell, A. H. Davidson, C. Earnshaw, H. K. Norrish, R. S. Torr, and S. Warren, J. Chem.

s4 J. M. Clough and G . Pattenden, Tetrahedron Lett., 1978, 4159.

J. Skolimowski and M. Simalty, Synthesis, 1979, 109.

1972, 1085.

SOC., Chem. Commun., 1978, 988.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

77 Phosphine Oxides and Related Compounds

0 II

But

MeOPBuf + [Bu'P-0 J H W

100%

(49) 52%

\ \

But

100%

Reagents: i, BusLi, at -78 "C; ii, CCh, at - 100 "C; iii, LDA; iv, heat (60 "C); v, MeOH;

iv,

BU'

Scheme 6

0 R 0 l l

%C=CHCH,CR + Ph,P6, N$ i-iv ") - Ii P&PCH,CH C

'0 (50)

Reagents: i , BuLi, THF; ii, RaCO; iii, NaH, THF; iv, heat.

Scheme 7

I i 20% (98%E-)

Reactions involving migration of a diphenylphosphinoyl group have been reviewed.36 Details have appeared of studies of the migratory aptitude of X or Ph,P(O) in the oxides (52; X=SPh, SMe, or OMe).36 The synthetic utility of 1,2-shifts of Ph,P(O)- units would seem to be limited to those where R1 is Ph,3e

s5 S . Warren, Acc. Chem. Res., 1978, 11, 401. 36 C. Earnshaw, J. I. Grayson, and S . Warren, J. Chern. SOC., Perkin Trans. 1 , 1979, 1506.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

78 Organophosphorus Chemistry 0 I I

PhzPH + R1+Yo 0

l l II 0 OH

ii. Ph2PCHR'CH2CRZ

ll I 0 ~ Ph,PCH R'CH2CH Rz

II Ph,P-eHR'

0 0 II I t

Ph,PCHRIC(OH)CH,RZ Ph,PCHR'CHMeCRZ

0 Reagents: i, &RZ ; ii, 0 0 3 ; iii, hRz ; iv, TFA; v, m-C1-CsHtCOaH; vi, BFa.

0

Scheme 8

as in the formation of (53). A neat synthesis of allylic alcohols relies on the reduction of the allylphosphine oxides (54) by LiAIH4.37 This process is regio- specific and highly stereoselective, and appears to rest on the hydroxy-group in (54) being able to direct the transfer of hydride to (54).a7

0 CH2R

TsOH in hot toluene II I PhzP-c-x X e SPh, R - p h PhzP I

Ph

(53) 50%

CHzR3 0

P h 2 ! p R 3 R' , Rfy 11

+ Ph,P' LIAIH,

RZ OH Rz OH

Epimeric alcohols are produced in the reduction by hydride or the ethynylation of the phosphorinanone derivatives (59, and they have been characterized by i.r. and n.m.r. spectr~scopy.~~ The [1,4]-azaphosphepine oxide (56) has been

1 7 R. R. Arndt and S. Warren, Tetrahedron Lett., 1978, 4089. a* Yu. G. Bosyakov, A. P. Logunov, B. M. Butin, and V. I. Artyukhin, J . Gen. Chcm. USSR

(Engl. Transl.) 1978, 48, 1189.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

Phosphine Oxides and Related Compounds 79

, CH

( 5 5 ) X = 0 or S

prepared as shown in Scheme 9. 3B Additions to acetyl(di-t-buty1)phosphine oxide (57) lead to the oxides (58) and (59).40 Other additions to similar oxides are discussed in Section 2 of this chapter.

(56) 40% overall

Reagents: i, HaNOH-HCI; ii, polyphosphoric acid; iii, NaH; iv, MeI.

Scheme 9

The a-diazophospholan l-oxide (60) has been ~haracterized,~' as shown in Scheme 10. Chloromethylation of the oxides (61) fails, except for the case where X is OMe, as

K. A. Petrov, V. A. Chauzov, N. Yu. Lebedeva, and S. M. Kostrova, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1078.

40 T. Kh. Gazizov, V. A. Kharlamov, and A. N. Pudovik, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1978, 1418.

41 M. Martin, M. Regitz, and M. Maas, Justus Liebigs Ann. Chem., 1978, 789. 4s U. V. Kormachev, Yu. N. Mitrasov, and V. A. Kukhtin, J. Gen. Chem. USSR (Engl.

Transl.), 1978, 48, 1079.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

80 Organophosphorus Chemistry

\ 0 Me I1 I /O

MeOPCH, C- C

Ph I Me I ‘CHN, 0’ ‘Ph

Reagents: i, TsN3, Et3N; ii, hv, PhNHz; iii, hv, benzene; iv, MeOH; v, PhsP. Scheme 10

0 0 Et

Et’ Et X = OMe only

(61) X = H, Me, or C1 70%

5 Physical and Structural Studies

X-Ray structure analysis43 of the oxides (62) reveals that the ‘endo’ oxide (62; R=Ph, X = 0) is the kinetic product of the trimerization44 leading to (62), and that it has a larger Rf value than (62; R = 0, X = Ph). The phosphetan rings of the oxides (63) have been shown by X-ray crystallography to be puckered.46

Ph -P R Me

R2 (63) R* = R2 = R3 = H

(62) 01 R’ = H, R2 = R3 = Me

43 W. Winter, Chem. Ber., 1978, 111, 2942. 44 W. Winter, Chem. Ber., 1976, 109, 2405. 45 A. Fitzgerald, J. A. Campbell, G. D. Smith, G. N. Laughlan, and S. E. Cremer, J. Org.

Chem.. 1978,43, 3513.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

Phosphine Oxides and Related Compounds

(65)47 and (66)48, and the selenides (67)49 and (68).48

81 Crystal structures have also been determined of the oxide (64),46 the sulphides

M e OH & (@P=S (WP=Se (65) R = H (67) R = H

od'ph

(64) (66) R = M e (68) R = M e

Dipole-moment data on phosphine oxides have been reviewed,50 and the dipole moments of the sulphides (69) have been The authors con- cluded that the P=S is not in the plane of an aromatic ring in (69), whereas in the oxides (70) the P=O group and the aromatic ring are coplanar.52

0 It

R,PAr

(69) R = H,Cl,Me,orOMe (70)

The diphosphine derivatives (71 ; R= Me) 53 and (72) 64 have been studied in detail by n.m.r., and the mass-spectral fragmentation of (71) has been described.6s The vibrational spectra of phosphine oxides have been reported for the series (73)58 and (74).67 Further structural study on the (perfluoroalky1)phosphine oxides (75) and their remarkably stable complexes with water and alcohols has been r e p ~ r t e d . ~ ~

The nature of the interaction of phosphine sulphides with metal salts and with halogens has been reviewed.59 Many papers have been devoted to a study of

46 S . E. Ealick, J. R. Baker, D. Van Der Helm, and K. D. Berlin, Acta Crystallogr., Sect. B,

47 P. W. Codding and K. A. Kerr, Acta Crystallogr., Sect. B, 1978, 34, 3785. 48 T. S. Cameron, K. D. Howlett, and K. Miller, Acta Crystallogr., Sect. B, 1978, 34, 1639. 49 P. W. Codding and K. A. Kerr, Acta Crystallogr., Sect. B, 1979, 35, 1261. 50 E. A. Ishmaeva, Rim. Chem. Rev. (Engl. Transl.), 1978, 47, 896. 51 S. B. Bulgarevich, L. V. Goncharova, 0. A. Osipov, V. V. Kesarev, and A. A. Shvets,

52 S. B. Bulgarevich, E. G. Amarskii, A. A. Shvets, and 0. A. Osipov, Zh. Obshch. Khirn.,

53 I. J. Colquhoun and W. McFarlane, J. Magn. Reson., 1978, 31, 63. s4 I. J. Colquhoun and W. McFarlane, J. Chem. Res. (S) , 1978, 368. 55 H. Keck and W. Kuchen, Org. Mass. Spectrom., 1979, 14, 149. 56 W. D. Burkhardt, E.-G. Hohn, and J. Goubeau, 2. Anorg. Allg. Chem., 1978,442, 19. 57 M. P. McDonald and L. D. Wilford, Spectrochim. Acta, Part A, 1978, 34, 933. 58 V. Ya. Semenii, V. N. Zavatskii, N. N. Kalibabchuk, E. V. Ryl'tsev, and V. V. Malovik,

80 E. W. Ainscough and A. M. Brodie, Coord. Chem. Rev., 1978,27, 59.

1979,35, 1107.

J . Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1219.

1976, 46, 1708.

J . Gen. Chem. USSR (Engl. Transl.). 1978, 48, 1213.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online

82

s s R2P-PR2

I1 II

Organophosphorus Chemistry

X

n = 1 o r 2

phosphine oxide or sulphide c o r n p l e ~ e s . ~ ~ - ~ ~ These include the oxides (76 ; R = Me) with ZnII salts,Bo (76; R=Et) with CoII salts,B1 (76; R=alkyl) with SnIV salts62 or with other metal and (76; R=Ph or NMe,) with TiIV derivative^.^

0 0 0 0

Diphosphine derivatives (77) and complexes with either lithium iong6 or uranyl ionBg have been investigated. The complexes of (71; R=Me) with copper@, cadmium, or nickel as the metal have been studied:? and it should be noted that THEY CAN BE EXPLOSIVE!87

The extraction of valuable metal ions by tri-n-octylphosphine oxide (78),88-70 by various alkylene oxides (77),71-74 and by other simple has been described.

60 Y. Hase and 0. L. Alves, J. Mol. Struct., 1978,50, 293. 61 J. Sznajder, A. Jablonski, and W. Wojciechowski, J. Inorg. Nucl. Chem., 1979, 41, 305. 69 I. P. Gol'dshtein, L. V. Kucheruk, E. D. Kremer, I. Ya. Kuramshin, E. N. Gur'yanova,

6* M. W. G. de Bolster, C. Boutkam, T. A. Van Der Knaap, L. Van Zweeden, I. E. Kortram,

64 R. C. Paul, P. K. Gupta, and S. L. Chadha, Indian J. Chem., Sect. A, 1978, 16,630. 6s V. G. Dashevskii, A. P. Baranov, T. Ya. Medved, and M. I. Kabachnik, Teor. Eksp. Khim.,

1978, 14, 488. ea T. Ya. Medved, N. P. Nesterova, P. V. Petrovskii, T. D. Kirillova, and M. I. Kabachnik,

Izv. Akad. Nauk SSSR, Ser. Khim., 1978, 1714. 0' G. D. McQuillan and I. A. Oxton, J , Chem. Soc., Dalton Trans, 1979, 895. a* M. Mojski, J. Radioanal. Chem., 1978, 46, 239. 6' M. Konstantinova, Dokl. Bolg. Akad. Nauk, 1978, 31, 101 1. 70 M. Konstantinova and I. Botev, Dokl. Bolg. Akad. Nauk, 1978, 31, 1321. T1 A. M. Rozen, 2. A. Berkman, L. E. Bertha, V. G. Kossykh, and K. S . Yudina, Zh. Neorg.

Khim., 1978, 23, 2474. M. K. Chmutova, N. E. Kochetkova, and B. F. Myasoedov, Radiokhimiya, 1978,20,713.

78 G. A. Pribylova, M. K. Chmutova, and B. F. Myasoedov, Radiokhimiya, 1978,20,719. T4 A. M. Rozen, Z. I. Nikolotova, N. A. Kartasheva, and A. S . Bol'shakova, Radiokhimiya,

75 A. M. Massabni, M. L. Gibran, and 0. A. Serra, Inorg. Nucl. Chern. Lett., 1978,14, 419.

and A. N. Pudovik, Izv. Akad. Nauk SSSR, Ser. Khim., 1978, 1825.

and W. L. Groeneveld, 2. Anorg. Allg. Chem., 1978,443, 269.

1978,20,725.

Dow

nloa

ded

by L

udw

ig M

axim

ilian

Uni

vers

itaet

on

04 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

14-0

0069

View Online