Experimental and theoretical studies of the hydrogenation of α,β-unsaturated acids by an 18 e hydride carbonylniobocene complex

Antonio Antiñolo, Khédidja Dorani, Santiago García-Yuste, Isabel López-Solera, Antonio Otero, María Teresa Tercero-Morales, Gábor Kovács, Gregori Ujaque, Agustí Lledós

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6 Citations (Scopus)

Abstract

The reaction of the niobocene complex [Nb(η5-C 5H4SiMe3)2(H)(CO)] (1) with α,β-unsaturated acids, namely, fumaric and maleic acids, and methylfumarate ester yielded the corresponding carboxylato-containing niobocene derivatives [Nb(η5-C5H4SiMe 3)2(κ1-O-OOC-CH2-CH 2-R)(CO)] (R = COOH (2); R = COOMe (3)), resulting from the hydrogenation of the C=C bond and the consequent coordination of a carboxylato moiety on the Nb center. The process represents the first reported example of the hydrogenation of α,β-unsaturated acids mediated by a hydride niobocene complex. Spectroscopic and theoretical studies at the DFT level have allowed for proposing a plausible reaction mechanism. Initial coordination of the C=C bond to the Nb center is followed by the insertion of this bond into the Nb-H bond, and the reaction is completed by a proton transfer from the carboxylic moiety to the α-carbon of the alkyl moiety, giving rise to the final κ1-carboxylato ligand. © 2012 American Chemical Society.
Original languageEnglish
Pages (from-to)5177-5184
JournalOrganometallics
Volume31
Issue number14
DOIs
Publication statusPublished - 23 Jul 2012

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