Organoosmium complexes of imidazole-containing chelate acceptor ligands

被引：4

作者：

Sarper, Orkan ^{[1
]}

Sarkar, Biprajit ^{[1
]}

Fiedler, Jan ^{[2
]}

Lissner, Falk ^{[1
]}

Kaim, Wolfgang ^{[1
]}

机构：

[1] Univ Stuttgart, Inst Anorgan Chem, D-70550 Stuttgart, Germany

[2] Acad Sci Czech Republ, J Heyrovsky Inst Phys Chem, VVI, CZ-18223 Prague, Czech Republic

来源：

INORGANICA CHIMICA ACTA | 2010年 / 363卷 / 12期

关键词：

Arene ligand; Electrochemistry; Electronic structure; Imidazole ligands; Osmium complexes; CRYSTAL-STRUCTURE; COORDINATION; REDUCTION; MONONUCLEAR; METAL; COPPER(II); GENERATION; PLATINUM; BIK; CU;

D O I：

10.1016/j.ica.2010.04.007

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complexes [(L)Os(eta(6)-Cym)Cl](PF6), Cym = p-cymene and L = bis(1-methylimidazol-2-yl) ketone (bik) or bis(1-methylimidazol-2-yl) glyoxal (big), were obtained and characterized with respect to spectroscopy, crystal structure (big complex) and (spectro)electrochemical behaviour at variable temperatures. DFT calculations confirm the structure of [(big)Os(eta(6)-Cym)Cl](+) with imidazolyl-N-bonded Os-II in a boat-shaped seven-membered chelate ring with small N-Os-N angles (<84 degrees). Reduction of this compound proceeds reversibly to a neutral complex of the alpha-semidione radical anion ligand big; EPR and IR spectroelectrochemistry indicate very little participation from the heavy metal in the spin distribution. The analogous [(bik)Os(eta(6)-Cym)Cl](+) could not be reduced reversibly to the ketyl radical complex but displayed a more reversible oxidation at high potential. (C) 2010 Elsevier B.V. All rights reserved.

引用

页码：3070 / 3077

页数：8

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