Os(H)2NO(PiPr3)2+:: Mechanism and energetics of a room temperature reversible ethyl/Hydridoethylene equilibrium and contrasting double insertion of acetylene

被引：15

作者：

Yandulov, DV ^{[1
]}

Bollinger, JC ^{[1
]}

Streib, WE ^{[1
]}

Caulton, KG ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 10期

关键词：

D O I：

10.1021/om000901g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

cis,trans-Os(H)(2)(NO)L-2(+) (L = (PPr3)-Pr-i) rapidly adds ethylene to give an eta (2)-ethylene complex with C2H4 trans to one hydride and cis to the other. One hydride and the four ethylene protons are exchanging reversibly above -20 degreesC, with a measured DeltaG(double dagger) (20 degreesC) of 15 kcal/mol. DFT calculations on the rearrangement reveal bond making and breaking, as well as migration of the nonexchanging hydride. Nitrosyl bending is not involved. Use of acetylene leads to insertion into both Os-H bonds; the resulting Os(CH=CH2)(2)(NO)L-2(+) was fully characterized as having inequivalent vinyl groups and undergoes facile vinyl ligand site exchange in solution.

引用

页码：2040 / 2046

页数：7

共 16 条

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