Formation of cationic half-sandwich osmium-vinylidene complexes from [OS(η5-C5H5)(PiPr3)2]+ and terminal alkynes

被引：37

作者：

Baya, M ^{[1
]}

Crochet, P ^{[1
]}

Esteruelas, MA ^{[1
]}

Lopez, AM ^{[1
]}

Modrego, J ^{[1
]}

机构：

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

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 20期

关键词：

D O I：

10.1021/om0104565

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ab initio calculations on the model complexes [Os(eta (5)-C5H5)(eta (2)-HC drop CH)(PH3)(2)](+) (1), [OsH(eta (5)-C5H5)-(C drop CH)(PH3)(2)](+) (2), and [Os(eta (5)-C5H5)(=C=CH2)(PH3)(2)](+) (3) indicate that the thermodynamic stability of these compounds decreases according to the sequence 3 > 1 > 2. According to this, the vinylidene complexes [Os(eta (C5H5)-C-5)(=C=CHR)((PPr3)-Pr-i)(2)]PF6 (R = Cy (8), Ph (9)) are prepared by deprotonation of [OsH(eta (5)-C5H5)(C drop CR)-((PPr3)-Pr-i)(2)]PF6 (R = Cy (4), Ph (5)) with KOH in methanol and subsequent protonation of the resulting alkynyl derivatives Os(eta (5) -C5H5)(C drop CR)((PPr3)-Pr-i)(2) (R = Cy (6), Ph (7)). The X-ray structure of [Os(eta (5)-C5H5)(=C=CHPh)-((PPr3)-Pr-i)(2)]PF6 (9) is also reported.

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页码：4291 / 4294

页数：4

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