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Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of "frustrated Lewis pairs".

ABSTRACT: The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH2P(t-C4H9)2)2C6H4) and acidic [LWH(CO)3] (L = Cp (1a), Tp (1b); Cp = η5-cyclopentadienyl, Tp = κ3-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)2(μ-CO)⋯Pd(PCP)] (4a, 4b), which catalyze amine-borane (Me2NHBH3, t BuNH2BH3) dehydrogenation. The combination of variable-temperature (1H, 31P{1H}, 11B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η1-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.

SUBMITTER: Osipova ES 

PROVIDER: S-EPMC8179527 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH<sub>2</sub>P(<i>t</i>-C<sub>4</sub>H<sub>9</sub>)<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>4</sub>) and acidic [LWH(CO)<sub>3</sub>] (L = Cp (<b>1a</b>), Tp (<b>1b</b>); Cp = η<sup>5</sup>-cyclopentadienyl, Tp = κ<sup>3</sup>-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)<sub>2</sub>(μ-CO)⋯Pd(PCP)] (<b>4a</b>, <b>4b</b>), which catalyze amine-borane (Me<sub>2</sub>NHBH<sub>3</sub>, <sup><i>t</i></sup>  ...[more]

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