The Mechanism of Alkene Addition to a Nickel Bis(dithiolene) Complex: The Role of the Reduced Metal Complex

被引：40

作者：

Dang, Li ^{[2
]}

Shibl, Mohamed F. ^{[3
]}

Yang, Xinzheng ^{[2
]}

Alak, Aiman ^{[1
]}

Harrison, Daniel J. ^{[1
]}

Fekl, Ulrich ^{[1
]}

Brothers, Edward N. ^{[3
]}

Hall, Michael B. ^{[2
]}

机构：

[1] Univ Toronto Mississauga, Mississauga, ON L5L 1C6, Canada

[2] Texas A&M Univ, Dept Chem, College Stn, TX 77842 USA

[3] Texas A&M Univ Qatar, Dept Chem, Doha, Qatar

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 10期

基金：

加拿大自然科学与工程研究理事会;

关键词：

COUPLED-CLUSTER SINGLES; DITHIOLENE COMPLEXES; BASIS-SET; OLEFINS; NI(S2C2(CF3)(2))(2); CYCLOADDITION; ETHYLENE; BINDING; ADDUCT; CCSD;

D O I：

10.1021/ja2107965

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The binding of an alkene by Ni(tfd)(2) [tfd = S2C2(CF3)(2)] is one of the most intriguing ligand-based reactions. In the presence of the anionic, reduced metal complex, the primary product is an interligand adduct, while in the absence of the anion, dihydrodithiins and metal complex decomposition products are preferred. New kinetic (global analysis) and computational (DFT) data explain the crucial role of the anion in suppressing decomposition and catalyzing the formation of the interligand product through a dimetallic complex that appears to catalyze alkene addition across the Ni-S bond, leading to a lower barrier for the interligand adduct.

引用

页码：4481 / 4484

页数：4

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