Hydride-carbyne to carbene transformation in a cyclopentadienyl-osmium complex:: An alternative to the single hydride-cα migration

被引：40

作者：

Baya, M ^{[1
]}

Esteruelas, MA ^{[1
]}

机构：

[1] Univ Zaragoza, Inst Ciencia Mat Aragon, Dept Quim Inorgan, E-50009 Zaragoza, Spain

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 11期

关键词：

D O I：

10.1021/om011077e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Complexes OsH(eta(5)-C5H5)(Cequivalent toCPh)(EPh3)-((PPr3)-Pr-i) [E = Si (1), Ge (2)] react with 2.0 equiv of HBF4.OEt2 to give [OsH(eta(5)-C5H5)(equivalent toC-CH2Ph)((PPr3)-Pr-i)]-BF4 (3). Treatment of 3 with KOH affords OsH(eta(5)-C5H5)(=C=CHPh)((PPr3)-Pr-i) (5) in equilibrium with the metalated species OsH(eta(5)-C5H5)(o-C6H4CH=CH)((PPr3)-Pr-i) (7) (DeltaHdegrees = -3.6 +/- 0.2 kcal mol(-1) and DeltaSdegrees = -10.8 +/- 1.9 cal K-1 mol(-1) for the formation of 7). The addition of P(OMe)3 to the solution of the isomeric mixture leads to Os(eta(5)-C5H5{(E)-CH=CHPh}{P(OMe)(3)}((PPr3)-Pr-i) (8), which reacts with HBF4.OEt2 to give [Os(eta(5)-C5H5(=CHCH2Ph){P(OMe)(3)}((PPr3)-Pr-i)]BF4 (4).

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页码：2332 / 2335

页数：4

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