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
收藏
页码：254 / 258
页数：5
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