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Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

TitlePreparation and reactivity of macrocyclic rhodium(III) alkyl complexes
Publication TypeJournal Article
Year of Publication2014
AuthorsCarraher, JM, Ellern, A, Bakac, A
JournalInorganica Chimica Acta
Date Published01
Type of ArticleArticle
ISBN Number0020-1693
Accession NumberWOS:000327531500010
KeywordsAlkylrhodium, 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

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.

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