Agostic versus Terminal Ethyl Rhodium Complexes: A Combined Experimental and Theoretical Study

被引：5

作者：

Geer, Ana M. ^{[1
,2
]}

Lopez, Jose A. ^{[1
]}

Ciriano, Miguel A. ^{[1
]}

Tejel, Cristina ^{[1
]}

机构：

[1] Univ Zaragoza, CSIC, ISQCH, Dept Quim Inorgan, Pedro Cerbuna 12, E-50009 Zaragoza, Spain

[2] Univ Nottingham, Sch Chem, Univ Pk, Nottingham NG7 2RD, England

来源：

ORGANOMETALLICS | 2016年 / 35卷 / 05期

基金：

奥地利科学基金会;

关键词：

C-H ACTIVATION; MIGRATORY INSERTION REACTIONS; BETA-HYDROGEN ELIMINATION; DENSITY-FUNCTIONAL THEORY; IN-PLACE ROTATION; BOND ACTIVATION; OLEFIN POLYMERIZATION; CHAIN PROPAGATION; ALKANE-DEHYDROGENATION; NONINNOCENT BEHAVIOR;

D O I：

10.1021/acs.organomet.6b00036

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ethylene insertion into RhH bonds in complexes bearing an anionic fac-triphosphane ligand gives hydrido complexes, beta-agostic species, or noninteracting ethyl derivatives depending on the reaction conditions. Several chemical equilibria between these species have been analyzed by NMR and DFT calculations, which revealed that they are mainly controlled by the entropy. Moreover, beta-agostic species were found to be lower in enthalpy than the corresponding hydrideethylene complexes, probably due to the steric pressure exerted by the bulky fac-triphosphane ligand.

引用

页码：799 / 808

页数：10

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