Journal of the Chemical Society, Dalton Transactions p. 3387 - 3396 (1996)
Update date:2022-09-26
Topics:
Brauers, Georg
Feher, Frank J.
Green, Michael
Hogg, John K.
Orpen, A. Guy
Reaction of the complex [Mo{η2(4e)-PhC2Ph}{P(OMe)3} 2(η-C5H5)][BF4]l with MgR(X) (R = Me, Et or PhCH2) afforded good yields of [Mo{η2(4e)-PhC2Ph}R{P(OMe)3}(η-C 5H5)], Unexpectedly, reaction of 1 with the 1,1-di-Grignard reagent CH2(MgI)2 gave the X-ray crystallographically identified zwitterionic complex [Mo{η2(4e)-PhC2Ph}{η2-P(OMe) 2OBF2OP(OMe)2}(η-C5H 5)], similar reactions with the but-2-yne and 1-phenylprop-2-yne complexes affording the analogous [Mo{η2(4e)-RC2R2){η 2-P(OMe)2OBF2OP(OMe)2}-(η-C 5H5)] (R = R2 = Me; R = Me, R2 = Ph). Treatment of the zwitterionic diphenylacetylene- and 1-phenylprop-2-yne-substituted complexes with K[BHBus3] gave the anionic η2(3e)-vinyl complexes K[Mo{=C(R)CH(Ph)}{η2-P(OMe)2OBF 2OP(OMe)2(η-C5H5)] (R = Ph or Me). Protonation (HBF4-Et2O) of the diphenyl-substituted η2(3e)-vinyl complex followed by addition of carbon monoxide, trimethyl phosphite, or diphenylacetylene afforded trans-stilbene and the complexes [Mo(CO)2 {η2-P(OMe)2OBF2OP(OMe) 2}-(η2-C5H5)], [Mo{P(OMe)3}2{η2-P(OMe)2OBF 2OP(OMe)2}(η-C5H5)] and [Mo{η2(4e)-PhC2Ph}{η2-P(OMe) 2OBF2OP(OMe)2}(η-C5H 5)] respectively. When CH2=CHCH2MgBr was added to 1 an unstable compound was formed, which on addition of P(OMe)3 gave [Mo{η3-C(Ph)=C(Ph)CH2CH=CH2}-{P(OMe) 3}2(η-C5H5)], the identity of which was confirmed by X-ray crystallography. This reaction is explained in terms of an unusual metalla-3,3-sigmatropic shift process. A similar reaction between 1 and CH2=CHMgBr followed by addition of P(OMe)3 surprisingly gave the η3-cyclopropenyl complex [Mo(η3-C3Ph2Me){P(OMe)3} 2(η-C5H5)]. The complex [Mo{η2(4e)-PhC2Ph}Me{P(OMe)3}-(η-C 5H5)] reacted thermally (78°C) with an excess of PhC2Ph to give the X-ray crystallographically identified complex [MoH(η4-C5H2Ph4){P(OMe) 3}(η-C5H5)], which on heating (100°C) afforded the dihydride [MoH2(η5-C5HPh4)(η-C 5H5)].
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()Doi:10.1021/jo961554g
(1996)
