An Acyl-NHC Osmium Cooperative System: Coordination of Small Molecules and Heterolytic B–H and O–H Bond Activation

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Title: An Acyl-NHC Osmium Cooperative System: Coordination of Small Molecules and Heterolytic B–H and O–H Bond Activation
Authors: Bolaño, Tamara | Esteruelas, Miguel A. | Gay, M. Pilar | Oñate, Enrique | Pastor, Isidro M. | Yus, Miguel
Research Group/s: Síntesis Asimétrica (SINTAS) | Nuevos Materiales y Catalizadores (MATCAT)
Center, Department or Service: Universidad de Alicante. Departamento de Química Orgánica | Universidad de Alicante. Instituto Universitario de Síntesis Orgánica
Keywords: Acyl-NHC Osmium Cooperative System | Small Molecules | Heterolytic B-H | O-H Bond Activation
Knowledge Area: Química Orgánica
Issue Date: 29-Jul-2015
Publisher: American Chemical Society
Citation: Organometallics. 2015, 34(15): 3902–3908. doi:10.1021/acs.organomet.5b00418
Abstract: The hexahydride complex OsH6(PiPr3)2 (1) activates the C–OMe bond of 1-(2-methoxy-2-oxoethyl)-3-methylimidazolium chloride (2), in addition to promoting the direct metalation of the imidazolium group, to afford a five-coordinate OsCl(acyl-NHC)(PiPr3)2 (3) compound. The latter coordinates carbon monoxide, oxygen, and molecular hydrogen to give the corresponding carbonyl (4), dioxygen (5), and dihydrogen (6) derivatives. Complex 3 also promotes the heterolytic bond activation of pinacolborane (HBpin), using the acyl oxygen atom as a pendant Lewis base. The hydride ligand and the Bpin substituent of the Fischer-type carbene of the resulting complex 7 activate the O–H bond of alcohols and water. As a consequence, complex 3 is a metal ligand cooperating catalyst for the generation of molecular hydrogen, by means of both the alcoholysis and hydrolysis of pinacolborane, via the intermediates 7 and 6.
Sponsor: Financial support from the MINECO of Spain (Projects CTQ2014-52799-P and CTQ2014-51912-REDC), the Diputación General de Aragón (E-35), and the European Social Fund (FSE) and FEDER. M.P.G. thanks the Spanish MINECO for her FPI fellowship. T.B. thanks the Spanish MINECO for funding through the Juan de la Cierva program.
ISSN: 0276-7333 (Print) | 1520-6041 (Online)
DOI: 10.1021/acs.organomet.5b00418
Language: eng
Type: info:eu-repo/semantics/article
Rights: This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Peer Review: si
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