Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

Journal Article · Sat Sep 21 04:00:00 EDT 2013 · Inorganica Chimica Acta

DOI:https://doi.org/10.1016/j.ica.2013.09.022· OSTI ID:1132295

Carraher, Jack M. ^[1]; Ellern, Arkady ^[2]; Bakac, Andreja ^[1]

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1. Ames Laboratory
2. Iowa State University

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.

• Research Organization: Ames Laboratory (AMES), Ames, IA (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: AC02-07CH11358
• OSTI ID: 1132295
• Report Number(s): IS-J 8198
• Journal Information: Inorganica Chimica Acta, Journal Name: Inorganica Chimica Acta Journal Issue: B Vol. 409; ISSN 0020-1693
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
AQUEOUS-SOLUTION
Alkylrhodium
RADICALS
bridged dicobaloximes
crystal-structure
hydrogen-atom transfer
kinetics
nmr
photochemical generation
photochemistry
structure-property relationship
synthesis
thermodynamics
variable-temperature h-1-nmr
x-ray