期刊
INORGANIC CHEMISTRY
卷 52, 期 14, 页码 8190-8201出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic400973t
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资金
- Council for Chemical Sciences of The Netherlands Organisation for Scientific Research
- NIOK Research Graduate School of Leiden University
- Dutch Universities
A systematic library of 24 nickel(II) complexes with bidentate diphosphane ligands was synthesized, and the solid-state structures of five of them were determined with X-ray crystallography. The compounds C1-C3 are common (P2NiX2)-X-II-type complexes, while C4 contains a unique [P2NiII(NH3)(OAc)](+) square-planar structure with a P2NO donor set and C5 constitutes a rare [(P2NiII)(2)(mu-OH)(2)](2+) dinuclear compound. The catalytic activity of all complexes was tested in the hydrogenation and/or isomerization of 1-octene in a CH2Cl2/CH3OH reaction medium. Catalyst precursors bearing ligands with o-alkoxy aryl rings selectively hydrogentate 1-octene to n-octane, while catalytic systems comprising ligands without the o-alkoxy functionality selectively isomerize the substrate to a mixture of internal alkenes, mostly cis- and trans-2-octene. The conversion is enhanced by equipping the ligand aryl rings with electron-donating alkoxy groups, by increasing the steric bulk of the backbone and/or the aryl rings, by employing relatively noncoordinating anions, and by adding a base as the cocatalyst. Using the compound [Ni(L3X)I-2] as the catalyst precursor and upon application of standard hydrogenation conditions, full conversion of the substrate was achieved in 1 h to isomerization products only (TON = 1940). When a catalytic amount of the base is added, a similar result is obtained even in the absence of H-2. A maximum TON of 4500 in 1 h with 96% selectivity for n-octane was achieved by employing [Ni(oMeO-L3X)(NH3)(OAc))]PF6 as the catalyst precursor.
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