C-H bond activation in aqueous solution: A linear free energy relationship investigation of the rate-limiting step in the EM exchange of alcohols catalyzed by a molybdocene

被引：27

作者：

Breno, KL ^{[1
]}

Tyler, DR ^{[1
]}

机构：

[1] Univ Oregon, Dept Chem, Eugene, OR 97403 USA

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 18期

关键词：

D O I：

10.1021/om010263h

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A biphasic linear free energy relationship was found for the H/D exchange reactions of the H atom bonded to the alpha -carbon atom in substituted benzyl alcohols catalyzed by [CP ' 2MoOH(OH2)](+) in aqueous solution. This observation is consistent with a rate-limiting step involving C-H oxidative addition. Two pathways for the C-H activation are proposed, one involving formation of a pi -bonded aldehyde and the other involving a sigma -bonded aldehyde. Donor groups favor the sigma -bonded intermediate and withdrawing groups the pi -bonded intermediate.

引用

页码：3864 / 3868

页数：5

共 20 条

[1]

[Anonymous], 1987, MECH THEORY ORGANIC

[2] SELECTIVE INTERMOLECULAR CARBON-HYDROGEN BOND ACTIVATION BY SYNTHETIC METAL-COMPLEXES IN HOMOGENEOUS SOLUTION [J].