期刊
ORGANOMETALLICS
卷 37, 期 16, 页码 2732-2740出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.8b00380
关键词
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资金
- MINECO of Spain [CTQ2017-82935-P, CTQ2016-81797-REDC]
- Diputacion General de Aragon [E06_17R]
- FEDER
- European Social Fund
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((PPr3)-Pr-i)(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(mu-OMe)(eta(4)-COD)](2) (COD = 1,5-cyclooctadiene) leads to Ir(2)(mu 4-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.
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