Hidden Noninnocence: Theoretical and Experimental Evidence for Redox Activity of a β-Diketiminate(1-) Ligand

被引：96

作者：

Khusniyarov, Marat M. ^{[1
,2
]}

Bill, Eckhard ^{[1
]}

Weyhermueller, Thomas ^{[1
]}

Bothe, Eberhard ^{[1
]}

Wieghardt, Karl ^{[1
]}

机构：

[1] Max Planck Inst Bioanorgan Chem, Stiftstr 34-36, D-45470 Mulheim, Germany

[2] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 07期

关键词：

chelates; density functional calculations; nickel; N ligands; redox chemistry; TRANSITION-METAL-COMPLEXES; PLANAR NICKEL-COMPLEXES; ELECTRONIC-STRUCTURES; RADICAL LIGANDS; SQUARE-PLANAR; NMR SHIFTS; COBALT; ACETYLACETONE; 3-COORDINATE; DERIVATIVES;

D O I：

10.1002/anie.201005953

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

End of innocence: A β-diketiminate(1-) ligand, formerly thought to be innocent, is shown to be redox-active: It can undergo one-electron oxidation to form a neutral π radical stabilized by coordination to a high-spin Ni II ion (see scheme). However, since the change in oxidation state of the ligand does not significantly change intraligand bond lengths, its noninnocence is hidden from X-ray crystallography. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：1652 / 1655

页数：4

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