Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry Article Swipe
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· 2018
· Open Access
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· DOI: https://doi.org/10.1021/acs.organomet.8b00687
· OA: W2903065021
Herein we describe the synthesis of a series of nickel complexes, including the formation of [(<sup>iPr</sup>PN<sup>H</sup>P)Ni(PMe<sub>3</sub>)][BPh<sub>4</sub>] (<sup>iPr</sup>PN<sup>H</sup>P = HN(CH<sub>2</sub>CH<sub>2</sub>(PiPr<sub>2</sub>))<sub>2</sub>). The ability of this phosphine complex to perform the 1,2-addition of H<sub>2</sub>O to produce the Ni–OH species [(<sup>iPr</sup>PN<sup>H</sup>P)NiOH][BPh<sub>4</sub>] has been investigated. The nucleophilicity of the hydroxide moiety of both [(iPrPNHP)NiOH][BPh4] and the previously reported (<sup>iPr</sup>PN<sup>H</sup>P)MnOH(CO)<sub>2</sub> was investigated through the hydration of aryl and alkyl nitriles, leading to the formation of a number of metal carboxamide (RC(O)NH–) bonds. This reactivity generated complexes with the general structures of [(<sup>iPr</sup>PN<sup>H</sup>P)Ni(NHC(O)R)][BPh<sub>4</sub>] for nickel and (<sup>iPr</sup>PN<sup>H</sup>P)Mn(NHC(O)R)(CO)<sub>2</sub> for manganese. Under catalytic conditions, the hydration of nitriles using nickel complexes yielded only a single turnover. However, (<sup>iPr</sup>PN<sup>H</sup>P)MnOH(CO)<sub>2</sub> produced several turnovers, and the reaction conditions were probed for optimization.
