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Franz, J.A. et al.

Franz, Birnbaum, Kolwaite, Linehan, Camaioni, Dupuis,

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

This paper provides evidence from kinetic experiments and electronic structure calculations of a significantly reduced S-H bond strength in the Mo(micro-SH)Mo function in the homogeneous catalyst model, CpMo(micro-S)(2)(micro-SH)(2)MoCp (1, Cp = eta(5)-cyclopentadienyl). The reactivity of 1 was explored by determination of a rate expression for hydrogen atom abstraction by benzyl radical from 1 (log(k(abs)/M(-)(1) s(-)(1)) = (9.07 +/- 0.38) - (3.62 +/- 0.58)/theta) for comparison with expressions for CH(3)(CH(2))(7)SH, log(k(abs)/M(-)(1) s(-)(1)) = (7.88 +/- 0.35) - (4.64 +/- 0.54)/theta, and for 2-mercaptonaphthalene, log(k(abs)/M(-)(1) s(-)(1)) = (8.21 +/- 0.17) - (4.24 +/- 0.26)/theta (theta = 2.303RT kcal/ mol, 2sigma 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(micro-S)(3)(micro-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.[1]

References

Activation of the sulfhydryl group by Mo centers: kinetics of reaction of benzyl radical with a binuclear Mo(micro-SH)Mo complex and with arene and alkane thiols. Franz, J.A., Birnbaum, J.C., Kolwaite, D.S., Linehan, J.C., Camaioni, D.M., Dupuis, M. J. Am. Chem. Soc. (2004) [Pubmed]

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