Synthesis and Reactivity of Nickel(II) Hydroxycarbonyl Species, NiCOOH-κC
作者： Changho Yoo , Jin Kim , Yunho Lee
DOI: 10.1021/OM400881J
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摘要: Reactions of nickel complexes supported by an anionic PNP pincer ligand (PNP– = N[2-PiPr2-4-Me-C6H3]2) toward CO2 and CO are investigated, particularly for interrogating their C–O bond formation/cleavage chemistry. The formation a formate species (2) was accomplished the reaction (PNP)NiH with CO2, while structural isomer complex (PNP)NiCOOH-κC (4) successfully produced from corresponding hydroxyl compound exposing it to CO(g). Its structurally unique character gleaned obtaining two solid-state structures {(PNP)Ni}2-μ-CO2-κ2C,O (6); latter obtained 4 complex. Both possess NiCOO-κC binding mode, which is reminiscent mode found at carbon monoxide dehydrogenase (CODH) active site its Ni–COO–Fe fragment. cationic {(PNP)NiCO}+ (7) also prepared via protonation 4, then led investigation in 7 ...
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