2024-03-28T17:33:35Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1692182019-08-09T04:30:39Zcom_10261_52707com_10261_5col_10261_52708
Base-free and acceptorless dehydrogenation of alcohols catalyzed by an iridium complex stabilized by a N,N,N-osmaligand
Alabau, Roberto G.
Esteruelas, Miguel A.
Martínez, Antonio
Oliván, Montserrat
Oñate, Enrique
Ministerio de Economía y Competitividad (España)
Agencia Estatal de Investigación (España)
European Commission
Diputación General de Aragón
The preparation of a N,N,N-osmaligand, its coordination to iridium to afford an efficient catalyst precursor, and the catalytic activity of the latter in dehydrogenation reactions of hydrogen carriers based on alcohols are reported. Complex OsH2Cl2(PiPr3)2 (1) reacts with 3-(2-pyridyl)pyrazol to give the osmium(II) complex 2H, which contains an acidic hydrogen atom. Deprotonation of the latter by the bridging methoxy groups of the dimer [Ir(μ-OMe)(η4-COD)]2 (COD = 1,5-cyclooctadiene) leads to Ir(2)(η4-COD) (3), where osmaligand 2 has a free-nitrogen atom. Iridium complex 3 catalyzes the dehydrogenation of secondary and primary alcohols to ketones and aldehydes or esters, respectively, and the dehydrogenation of diols to lactones. Cyclooctatriene is detected during the catalysis by GC-MS, suggesting that the true catalyst of the reactions is a dihydride IrH2(2)-species with osmaligand 2 acting as N,N,N-pincer. The presence of a phenyl group in the substrates favors the catalytic processes. The dehydrogenative homocoupling of primary alcohols to esters appears to take place via the transitory formation of hemiacetals.
2018-08-29T07:35:28Z
2018-08-29T07:35:28Z
2018
artículo
Organometallics 37(16): 2732-2740 (2018)
0276-7333
http://hdl.handle.net/10261/169218
10.1021/acs.organomet.8b00380
1520-6041
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100011033
eng
Postprint
https://doi.org/10.1021/acs.organomet.8b00380
Sí
CTQ2017-82935-P/AEI/10.13039/501100011033
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-82935-P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-81797-REDC
openAccess
American Chemical Society