The Ir(III) compound TpMe 2Ir[C(CO 2Me)= C(CO 2Me)C(CO 2Me)=C(CO 2Me)](OH 2) (1) reacts thermally with aliphatic aldehydes RC(O)H (R = Me, tBu) to lead to the decarbonylation products TpMe 2Ir[C(CO 2Me)=C- (CO 2Me)C(CO 2Me)=C(CO 2Me)](CO) (2) and RH. In turn, formaldehyde reacts with 1, yielding a product resulting from the hydrogenation of one of the double bonds of the iridacycle. Theoretical calculations reveal the role of the metallacycle as a shuttle for the transfer of the aldehyde H atom. Under photochemical (UV) irradiation, the decarbonylation reaction becomes catalytic for a variety of aliphatic aldehydes. © 2012 American Chemical Society.

Financial support (FEDER and ESF contribution) from the Spanish Ministry of Science (Projects CTQ2010-17476, CTQ2008-00810, and Consolider-Ingenio 2010 CSD2007- 00006), the Junta de Andalucía (Grant FQM-119 and Project P09-FQM-4832), the Diputación General de Aragón (E35), and the CONACYT-México (Grants 025424 and 84453 and scholarship to A.E.R.) is gratefully acknowledged. J.L.-S. is thankful to the Spanish Ministry of Science and Innovation (MICINN) for a Ramón y Cajal Contract.

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