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Issue 8, 2010
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Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe3)2(CO)H and its role in proton transfer

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Abstract

The interaction of the carbonyl hydride complex Cp*Mo(PMe3)2(CO)H with Brønsted (fluorinated alcohols, (CF3)nCH3−nOH (n = 1–3), and CF3COOH) and Lewis (Hg(C6F5)2, BF3·OEt2) acids was studied by variable temperature IR and NMR (1H, 31P, 13C) spectroscopies in combination with DFT/B3LYP calculations. Among the two functionalities potentially capable of the interaction – carbonyl and hydride ligands – the first was found to be the preferential binding site for weak acids, yielding COHOR or COHg complexes as well as CO(HOR)2 adducts. For stronger proton donors ((CF3)3COH, CF3COOH) hydrogen-bonding to the hydride ligand can be revealed as an intermediate of the proton transfer reaction. Whereas proton transfer to the CO ligand is not feasible, protonation of the hydride ligand yields an (η2-H2) complex. Above 230 K dihydrogen evolution is observed leading to decomposition. Among the decomposition products compound [Cp*Mo(PMe3)3(CO)]+[(CF3)3CO·2HOC(CF3)3] resulting from a phosphine transfer reaction was characterized by X-ray diffraction. Reaction with BF3·OEt2 was found to produce [Cp*Mo(PMe3)2(CO)BF4] via initial attack of the hydride ligand.

Graphical abstract: Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe3)2(CO)H and its role in proton transfer

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Publication details

The article was received on 05 Aug 2009, accepted on 25 Nov 2009 and first published on 11 Jan 2010


Article type: Paper
DOI: 10.1039/B916084A
Citation: Dalton Trans., 2010,39, 2008-2015
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    Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe3)2(CO)H and its role in proton transfer

    P. A. Dub, O. A. Filippov, N. V. Belkova, J. Daran, L. M. Epstein, R. Poli and E. S. Shubina, Dalton Trans., 2010, 39, 2008
    DOI: 10.1039/B916084A

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