Aqueous phase organometallic catalysis using (MeCp)2Mo(OH)(H2O)+.: Intramolecular attack of hydroxide on organic substrates

被引：50

作者：

Breno, KL ^{[1
]}

Pluth, MD ^{[1
]}

Landorf, CW ^{[1
]}

Tyler, DR ^{[1
]}

机构：

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

来源：

ORGANOMETALLICS | 2004年 / 23卷 / 08期

关键词：

D O I：

10.1021/om0342558

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The hydrolysis of esters and difunctional ethers catalyzed by Cp'Mo-2(OH)(H2O)(+) (1) (Cp' = eta(5)-C5H4CH3) and the stoichiometric oxidation of CO to CO2 in the presence of 1 are described. These reactions, combined with the previously reported nitrile hydrations and phosphate esters hydrolyses catalyzed by 1, demonstrate that 1 is an effective homogeneous catalyst for hydration, hydrolysis, and oxidation reactions in aqueous solution under mild conditions (pH similar to7, similar to80 degreesC). Each reaction is proposed to proceed by intramolecular attack of the hydroxide ligand on a bound substrate. The intramolecular nature of the reaction is supported by the ester hydrolysis activation parameters (DeltaH(double dagger) = 5.9 +/- 0.7 kcal/mol and DeltaS(double dagger) = -48 +/- 9 eu), the lack of H/D exchange, and the significant increase (10(6)-10(8)) in the rate of hydrolysis over uncatalyzed hydrolysis.

引用

页码：1738 / 1746

页数：9

共 49 条

[1] Isolation and crystal structure of a water-soluble iridium hydride: A robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds in acidic media [J].