Alkyne insertion into the Ru-C bond of a four-membered metallacycle. Insertion rate and reaction pathway

被引：27

作者：

Ghosh, K ^{[1
]}

Chattopadhyay, S ^{[1
]}

Pattanayak, S ^{[1
]}

Chakravorty, A ^{[1
]}

机构：

[1] Indian Assoc Cultivat Sci, Dept Inorgan Chem, Kolkata 700032, W Bengal, India

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 07期

关键词：

D O I：

10.1021/om000649c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The insertion of HOCH2C drop CH (ha) into the Ru-C bond of Ru-II(RL1)(PPh3)(2)(CO)Cl, 1, has afforded Ru-II(RL3)(PPh3)(2)(CO)Cl, 3, which has been structurally characterized. Insertion rates in CH2Cl2-MeOH for ha as well as for PhC drop CH (pa), which inserts similarly into 1 affording Ru-II(RL2)(PPh3)(2)(CO)Cl, 2, are proportional to the product of the concentrations of alkyne and methanol. The insertion rate of ha is nearly 5 times faster than that of pa, and for a given alkyne the rate increases as R becomes more electron-withdrawing (OMe < Me < Cl). A reaction model implicating the adduct 1 . MeOH, which binds and activates the alkyne via displacement of MeOH, is proposed.

引用

页码：1419 / 1423

页数：5

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