Activation of the sulfhydryl group by Mo centers: Kinetics of reaction of benzyl radical with a binuclear Mo(μ-SH)Mo complex and with arene and alkane thiols

James A. Franz, Jerome C. Birnbaum, Douglas S. Kolwaite, John Linehan, Donald M. Camaioni, Michel Dupuis

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This paper provides evidence from kinetic experiments and electronic structure calculations of a significantly reduced S-H bond strength in the Mo(μ-SH)Mo function in the homogeneous catalyst model, CpMo(μ-S) 2(μ-SH)2MoCp (1, Cp = η 5-cyclopentadienyl). The reactivity of 1 was explored by determination of a rate expression for hydrogen atom abstraction by benzyl radical from 1 (log(kabs/M-1 s-1) = (9.07 ± 0.38) - (3.62 ± 0.58)/θ) for comparison with expressions for CH3(CH2)7SH, log(kabs/M -1 s-1) = (7.88 ± 0.35) - (4.64 ± 0.54)/θ, and for 2-mercaptonaphthalene, log(kabs/M -1 s-1) = (8.21 ± 0.17) - (4.24 ± 0.26)/θ (θ = 2.303RT kcal/mol, 2σ error). The rate constant for hydrogen atom abstraction at 298 K by benzyl radical from 1 is 2 orders of magnitude greater than that from 1-octanethiol, resulting from the predicted (DFT) S-H bond strength of 1 of 73 kcal/mol. The radical CpMo(μ-S) 3(μ-SH)MoCp, 2, is revealed, from the properties of slow self-reaction, and exclusive cross-combination with reactive benzyl radical, to be a persistent free radical.

Original languageEnglish
Pages (from-to)6680-6691
Number of pages12
JournalJournal of the American Chemical Society
Issue number21
Publication statusPublished - Jun 2 2004


ASJC Scopus subject areas

  • Chemistry(all)

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