A BIMETALLIC HYDROFORMYLATION CATALYST - HIGH REGIOSELECTIVITY AND REACTIVITY THROUGH HOMOBIMETALLIC COOPERATIVITY

被引：288

作者：

BROUSSARD, ME ^{[1
]}

JUMA, B ^{[1
]}

TRAIN, SG ^{[1
]}

PENG, WJ ^{[1
]}

LANEMAN, SA ^{[1
]}

STANLEY, GG ^{[1
]}

机构：

[1] LOUISIANA STATE UNIV,DEPT CHEM,BATON ROUGE,LA 70803

来源：

SCIENCE | 1993年 / 260卷 / 5115期

关键词：

D O I：

10.1126/science.260.5115.1784

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The racemic and meso diastereomers of an electron-rich binucleating tetraphosphine ligand have been used to prepare homobimetallic rhodium norbornadiene complexes. The racemic bimetallic Rh complex is an excellent hydroformylation catalyst for 1-alkenes, giving both a high rate of reaction and high regioselectivity for linear aldehydes, whereas the meso complex is considerably slower and less selective. A mechanism involving bimetallic cooperativity between the two rhodium centers in the form of an intramolecular hydride transfer is proposed. Mono- and bimetallic model complexes in which the possibility for bimetallic cooperativity has been reduced or eliminated are very poor catalysts.

引用

页码：1784 / 1788

页数：5

共 43 条

[1] A COMPARISON OF FACE-CAPPING VERSUS FRAGMENTATION REACTIONS OF [RH4(CO)12] WITH TRIPHOS, (MEC(CH2PPH2)3) AND TRIPOD, (HC(PPH2)3) - CRYSTAL-STRUCTURE OF [(TRIPHOS)RH(MU-CO)2RH(TRIPHOS)] [J].