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Issue 23, 2014
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Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(V)-oxo species

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Abstract

Photo-disproportionation of a bis-porphyrin-diruthenium(IV) μ-oxo dimer gave a porphyrin-ruthenium(III) species and a putative porphyrin-ruthenium(V)-oxo species that can be detected and studied in real time via laser flash photolysis methods. As determined by its spectral and kinetic behavior, the same oxo transient was also formed by photolysis of a porphyrin-ruthenium(III) N-oxide adduct. Second-order rate constants for reactions with several substrates at 22 °C were determined; representative values of rate constants were kox = 6.6 × 103 M−1 s−1 for diphenylmethanol, kox = 2.5 × 103 M−1 s−1 for styrene, and kox = 1.8 × 103 M−1 s−1 for cyclohexene. The putative porphyrin-ruthenium(V)-oxo transient reacted 5–6 orders of magnitude faster than the corresponding trans-dioxoruthenium(VI) porphyrins, and the rate constants obtained in this work were similar to those of the corrole-iron(V)-oxo derivative. The high reactivity for the photochemically generated ruthenium-oxo species in comparison to other porphyrin-metal-oxo intermediates suggests that it is a true ruthenium(V)-oxo species.

Graphical abstract: Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(v)-oxo species

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Publication details

The article was received on 03 Mar 2014, accepted on 03 Apr 2014 and first published on 03 Apr 2014


Article type: Paper
DOI: 10.1039/C4DT00649F
Citation: Dalton Trans., 2014,43, 8749-8756
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    Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(V)-oxo species

    R. Zhang, E. Vanover, W. Luo and M. Newcomb, Dalton Trans., 2014, 43, 8749
    DOI: 10.1039/C4DT00649F

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