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Dub PA, Filippov OA, Belkova NV, et al. Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer. Dalton Trans. 2010;39(8):2008-15doi: 10.1039/b916084a.
Dub, P. A., Filippov, O. A., Belkova, N. V., Daran, J. C., Epstein, L. M., Poli, R., & Shubina, E. S. (2010). Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer. Dalton transactions (Cambridge, England : 2003), 39(8), 2008-15. https://doi.org/10.1039/b916084a
Dub, Pavel A, et al. "Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer." Dalton transactions (Cambridge, England : 2003) vol. 39,8 (2010): 2008-15. doi: https://doi.org/10.1039/b916084a
Dub PA, Filippov OA, Belkova NV, Daran JC, Epstein LM, Poli R, Shubina ES. Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer. Dalton Trans. 2010 Feb 28;39(8):2008-15. doi: 10.1039/b916084a. Epub 2010 Jan 11. PMID: 20148218.
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Dalton Trans. 2010 Feb 28;39(8):2008-15. doi: 10.1039/b916084a. Epub 2010 Jan 11.

Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer.

Dalton transactions (Cambridge, England : 2003)

Pavel A Dub, Oleg A Filippov, Natalia V Belkova, Jean-Claude Daran, Lina M Epstein, Rinaldo Poli, Elena S Shubina

Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, 119991, Moscow, Russia.

PMID: 20148218 DOI: 10.1039/b916084a

Abstract

The interaction of the carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H with Brønsted (fluorinated alcohols, (CF(3))(n)CH(3-n)OH (n = 1-3), and CF(3)COOH) and Lewis (Hg(C(6)F(5))(2), BF(3).OEt(2)) acids was studied by variable temperature IR and NMR ((1)H, (31)P, (13)C) 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 CO...HOR or CO...Hg complexes as well as CO...(HOR)(2) adducts. For stronger proton donors ((CF(3))(3)COH, CF(3)COOH) 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 (eta(2)-H(2)) complex. Above 230 K dihydrogen evolution is observed leading to decomposition. Among the decomposition products compound [Cp*Mo(PMe(3))(3)(CO)](+)[(CF(3))(3)CO.2HOC(CF(3))(3)](-) resulting from a phosphine transfer reaction was characterized by X-ray diffraction. Reaction with BF(3).OEt(2) was found to produce [Cp*Mo(PMe(3))(2)(CO)BF(4)] via initial attack of the hydride ligand.

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