Modulating Sterics in Trimethylplatinum(IV) Diimine Complexes To Achieve C-C Bond-Forming Reductive Elimination

被引：30

作者：

Lanci, Michael P. ^{[2
]}

Remy, Matthew S. ^{[1
]}

Lao, David B. ^{[2
]}

Sanford, Melanie S. ^{[1
]}

Mayer, James M. ^{[2
]}

机构：

[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA

[2] Univ Washington, Dept Chem, Seattle, WA 98195 USA

来源：

ORGANOMETALLICS | 2011年 / 30卷 / 14期

关键词：

ELECTROPHILIC PLATINUM COMPLEXES; CARBON-CARBON; H ACTIVATION; COUPLING REACTIONS; ETHANE; PT(IV); OXIDATION; ALKYL; LIGANDS; METHANE;

D O I：

10.1021/om200508k

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Tuning the aryl substituents of N,N'-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (DAB) ligands promotes the challenging C-C bond-forming reductive elimination from Pt-IV diimine complexes [(DAB)Pt(CH3)(3)(solvent)](+) (2) under mild conditions. Experimental results and density functional calculations indicate that 2,6-aryl substitution promotes reductive elimination by facilitating dissociation of the coordinating solvent by close to 10 kcal mol(-1), but too much steric bulk inhibits the formation of 2 in the one-electron outersphere oxidation of (DAB)Pt(CH3)(2) (1).

引用

页码：3704 / 3707

页数：4

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