Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry
| Autor: | James M. Boncella, Nickolas H. Anderson, Aaron M. Tondreau |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Nitrile
010405 organic chemistry Chemistry Organic Chemistry chemistry.chemical_element 010402 general chemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences Catalysis Inorganic Chemistry chemistry.chemical_compound Nickel Transition metal Moiety Hydroxide Reactivity (chemistry) Physical and Theoretical Chemistry Phosphine |
| Zdroj: | Organometallics. 37:4675-4684 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/acs.organomet.8b00687 |
| Popis: | Herein we describe the synthesis of a series of nickel complexes, including the formation of [(iPrPNHP)Ni(PMe3)][BPh4] (iPrPNHP = HN(CH2CH2(PiPr2))2). The ability of this phosphine complex to perform the 1,2-addition of H2O to produce the Ni–OH species [(iPrPNHP)NiOH][BPh4] has been investigated. The nucleophilicity of the hydroxide moiety of both [(iPrPNHP)NiOH][BPh4] and the previously reported (iPrPNHP)MnOH(CO)2 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 [(iPrPNHP)Ni(NHC(O)R)][BPh4] for nickel and (iPrPNHP)Mn(NHC(O)R)(CO)2 for manganese. Under catalytic conditions, the hydration of nitriles using nickel complexes yielded only a single turnover. However, (iPrPNHP)MnOH(CO)2 produced several turnovers, and the reaction conditions were probed for optimization. |
| Databáze: | OpenAIRE |
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