Agostic Interactions in Nickel(II) Complexes: Trans Influence of Ancillary Ligands on the Strength of the Bond

被引：20

作者：

Pudasaini, Bimal ^{[1
]}

Janesko, Benjamin G. ^{[1
]}

机构：

[1] Texas Christian Univ, Dept Chem, Box 298860, Ft Worth, TX 76129 USA

来源：

ORGANOMETALLICS | 2014年 / 33卷 / 01期

关键词：

N-HETEROCYCLIC CARBENE; CROSS-COUPLING REACTIONS; CORRELATED MOLECULAR CALCULATIONS; EFFECTIVE CORE POTENTIALS; BASIS-SET CONVERGENCE; GAUSSIAN-BASIS SETS; ELECTRONIC-STRUCTURE; DENSITY FUNCTIONALS; THERMOCHEMICAL KINETICS; REDUCTIVE ELIMINATION;

D O I：

10.1021/om400731j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The selectivity of transition-metal-catalyzed alkyl cross-coupling is significantly affected by agostic interactions. We report a systematic computational study of how ligand trans influence affects the strength of beta-agostic interactions in Ni(II)-ethyl complexes selected to model cross-coupling intermediates. The roles of pi back-donation and in-plane pi coupling are highlighted. Calculations with carbene ligands illustrate the relevance of these ideas for ligand design.

引用

页码：84 / 93

页数：10

共 136 条

[1] Structural, spectroscopic, and theoretical elucidation of a redox-active pincer-type ancillary applied in catalysis [J].