Journal article

Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic (MoO)-O-V(mu-S)Cu-I complexes

Craig Gourlay, David J Nielsen, David J Evans, Jonathan M White, Charles G Young

Chemical Science | Royal Society of Chemistry | Published : 2018

Abstract

Reaction of [CoCp2][TpiPrMoOS(OAr)] [Cp = η5-cyclopentadienyl; TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate; OAr = phenolate or derivative thereof] with [Cu(NCMe)(Me3tcn)]BF4 (Me3tcn = 1,4,7-trimethyl-1,4,7-triazacyclononane) in MeCN at −30 °C results in the formation of red-brown/black, paramagnetic, μ-sulfido-Mo(V)/Cu(I) complexes, TpiPrMoO(OAr)(μ-S)Cu(Me3tcn). The complexes possess the MoO(μ-S)Cu core found in aerobic carbon monoxide dehydrogenases (CODHs) and exhibit X-band EPR spectra closely related to those of semi-reduced CODH, with giso ∼ 1.937, hyperfine coupling to 95,97Mo (aiso = 39–42 × 10−4 cm−1) and strong superhyperfine coupling to 63,65Cu (aiso = 34–63 × 10−4 cm−1). Anis..

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University of Melbourne Researchers

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Funding Acknowledgements

We thank Ms Sioe See Volaric for mass spectrometric results, Dr Stephen P. Best for invaluable assistance with the EPR studies and Profs Martin L. Kirk (University of New Mexico) and Graham N. George (University of Saskatchewan) for sharing unpublished results and insights. We gratefully acknowledge the financial support of the Australian Research Council, the donors of the Petroleum Research Fund (administered by the American Chemical Society) and the Albert Shimmins Writing Up Award (to CG).