Journal
CHEMICAL SCIENCE
Volume 12, Issue 10, Pages 3682-3692Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0sc06114j
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Funding
- Russian Science Foundation [19-13-00459]
- bilateral project CNR (Italy) RFBR (Russian Federation) 2018-2020 [18-53-7818]
- Ministry of Science and Higher Education of the Russian Federation
- Russian Science Foundation [19-13-00459] Funding Source: Russian Science Foundation
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The reaction between basic [(PCP)Pd(H)] and acidic [LWH(CO)(3)] leads to the formation of bimolecular complexes that catalyze dehydrogenation. Experimental and computational studies reveal the formation of a complex in the first step, where proton transfer is the rate-determining step.
The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH2P(t-C4H9)(2))(2)C6H4) and acidic [LWH(CO)(3)] (L = Cp (1a), Tp (1b); Cp = eta(5)-cyclopentadienyl, Tp = kappa(3)-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)(2)(mu-CO)MIDLINE HORIZONTAL ELLIPSISPd(PCP)] (4a, 4b), which catalyze amine-borane (Me2NHBH3, (BuNH2BH3)-Bu-t) dehydrogenation. The combination of variable-temperature (H-1, P-31{H-1}, B-11 NMR and IR) spectroscopies and computational (omega B97XD/def2-TZVP) studies reveal the formation of an eta(1)-borane complex [(PCP)Pd(Me2NHBH3)](+)[LW(CO3)](-) (5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species 4 are easily regenerated through hydrogen evolution in the reaction between two hydrides.
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