Inorganic Chemistry p. 1374 - 1380 (1973)
Update date:2022-08-05
Topics:
Cavell
Leary
Sanger
Tomlinson
The esters R2PESi(CH3)3 (R = F, E = O; R = CF3, E = O, S) have been prepared using one or more of four synthetic routes (CF3)2PSSi(CH3)3 is the first known example of a PIII-S-Si bridged compound, but the analogous difluoro ester F2PSSi(CH3)3 appears to be thermally unstable at 25°. Attempted syntheses of the P(V) isomers R2P(E)Si(CH3)3 gave only the P(III) forms, indicating that these systems are susceptible to anti-Arbuzov rearrangements. The difference in the stability and polarity between the P-O-Si and P-S-Si bridge units was demonstrated by the reactions of the esters with HCl and (CH3)2NH. At least three different reactions of the esters with dimethylamine were observed: cleavage at the E-Si bond with or without concomitant subsequent reaction of (CH3)3SiN(CH3)2 with the ionic product R2PE- and, in the case of (CF3)2POSi(CH3)3, displacement of CF3H to yield CF3[N(CH3)2]POSi(CH3)3. The latter phosphine showed a temperature-dependent nmr spectrum consistent with conformational isomerism of the N(CH3)2 group.
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Doi:10.1016/0040-4020(73)80164-4
(1973)Doi:10.1246/bcsj.45.2822
(1972)Doi:10.1007/BF00772879
()Doi:10.1016/S0040-4020(99)00272-0
(1999)Doi:10.1021/ol0168364
(2001)Doi:10.1016/S0008-6215(01)00222-1
(2001)
