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Title: Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

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.
 [1] ;  [2] ;  [1]
  1. Ames Laboratory
  2. Iowa State University
Publication Date:
OSTI Identifier:
Report Number(s):
IS-J 8198
Journal ID: ISSN 0020-1693
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganica Chimica Acta; Journal Volume: 409; Journal Issue: B
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
36 MATERIALS SCIENCE Alkylrhodium, AQUEOUS-SOLUTION, bridged dicobaloximes, crystal-structure, hydrogen-atom transfer, kinetics, nmr, photochemical generation, photochemistry, RADICALS, structure-property relationship, synthesis, thermodynamics, variable-temperature h-1-nmr, x-ray