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Title

Sequential and selective hydrogenation of the Cα−Cβ and M−Cα double bonds of an allenylidene ligand coordinated to osmium: New reaction patterns between an allenylidene complex and alcohols

AuthorsBolaño, Tamara CSIC; Castarlenas, Ricardo CSIC ORCID; Esteruelas, Miguel A. CSIC ORCID; Oñate, Enrique CSIC ORCID
Issue DateJun-2007
PublisherAmerican Chemical Society
CitationJournal of the American Chemical Society 129(28): 8850-8859 (2007)
AbstractComplex [OsH(CCCPh2)(CH3CN)2(PiPr3)2]BF4 (1) reacts with primary and secondary alcohols to give the corresponding dehydrogenated alcohols and the hydride-carbene derivative [OsH(CHCHCPh2)(CH3CN)2(PiPr3)2]BF4 (2), as a result of hydrogen transfer reactions from the alcohols to the Cα−Cβ double bond of the allenylidene ligand of 1. The reactions with phenol and t-butanol, which do not contain any β-hydrogen, afford the alkoxy-hydride-carbyne complexes [OsH(OR)(CCHCPh2)(CH3CN)(PiPr3)2]BF4 (R = Ph (3), tBu (4)), as a consequence of the 1,3-addition of the O−H bond of the alcohols to the metallic center and the Cβ atom of the allenylidene of 1. On the basis of the reactions of 1 with these tertiary alcohols, deuterium labeling experiments, and DFT calculations, the mechanism of the hydrogenation is proposed. In acetonitrile under reflux, the Os−C double bond of 2 undergoes hydrogenation to give 1,1-diphenylpropene and ¢Sq = -43.5 +/- 9.6 J mol-1 K-1. The X-ray structures of 2 and 3 are also reported.
Description10 pages, 5 figures, 4 schemes.-- Supporting Information Available: http://pubs.acs.org.
Publisher version (URL)http://dx.doi.org/10.1021/ja071972a
URIhttp://hdl.handle.net/10261/19479
DOI10.1021/ja071972a
ISSN0002-7863
Appears in Collections:(ICMA) Artículos

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