Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

被引：1

作者：

Carraher, Jack M. ^{[1
,2
]}

Ellern, Arkady ^{[2
]}

Bakac, Andreja ^{[1
,2
]}

机构：

[1] Iowa State Univ, Ames Lab, Ames, IA 50011 USA

[2] Iowa State Univ, Dept Chem, Ames, IA 50011 USA

来源：

INORGANICA CHIMICA ACTA | 2014年 / 409卷

基金：

美国国家科学基金会;

关键词：

Alkylrhodium; Synthesis; X-ray; NMR; Photochemistry; HYDROGEN-ATOM TRANSFER; PHOTOCHEMICAL GENERATION; CRYSTAL-STRUCTURE; KINETICS; THERMODYNAMICS; NONEQUIVALENCE; HOMOLYSIS; MECHANISM; RADICALS; HYDRIDES;

D O I：

10.1016/j.ica.2013.09.022

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Macrocyclic rhodium(II) complexes LRh(H2O)(2+) (L = L-1 = cyclam and L-2 = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH3)(2)OOH to generate the corresponding rhodium(III) alkyls L(H2O)RhR2+ (R = CH3, C2H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgH)(2)(H2O) CoR and (dmgBF(2))(2)(H2O) CoR (R = CH3, PhCH2) to LRh(H2O)(2+). The new complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis. (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：254 / 258

页数：5

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