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

We found that the macrocyclic rhodium(II) complexes LRh(H2O)2+ (L = L1 = cyclam and L2 = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH3)2OOH 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 (dmgBF2)2(H2O) CoR (R = CH3, PhCH2) to LRh(H2O)2+. Moreover, 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.
 [1] ;  [2] ;  [1]
  1. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
IS--J 8213
Journal ID: ISSN 0020-1693
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganica Chimica Acta; Journal Volume: 409
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