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An Acyl-NHC osmium cooperative system: Coordination of small molecules and heterolytic B-H and O-H bond activation

AuthorsBolaño, Tamara ; Esteruelas, Miguel A. ; Gay, M. Pilar ; Oñate, Enrique ; Pastor, Isidro M.; Yus, Miguel
Issue Date2015
PublisherAmerican Chemical Society
CitationOrganometallics 34(15): 3902-3908 (2015)
AbstractThe hexahydride complex OsH6(PiPr3)2 activates the C−OMe bond of 1-(2-methoxy-2-oxoethyl)-3-methylimidazolium chloride, in addition to promoting the direct metalation of the imidazolium group, to afford a fivecoordinate OsCl(acyl-NHC)(PiPr3)2 compound. The latter coordinates carbon monoxide, oxygen, and molecular hydrogen to give the corresponding carbonyl, dioxygen, and dihydrogen 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.
DescriptionThis is an open access article published under an ACS AuthorChoice License.
Publisher version (URL)http://dx.doi.org/10.1021/acs.organomet.5b00418
Identifiersdoi: 10.1021/acs.organomet.5b00418
issn: 0276-7333
e-issn: 1520-6041
Appears in Collections:(ISQCH) Artículos
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