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The zerovalent nickel complex, (triphos)Ni(PPh 3 ), is quantitatively alkylated by a methylcobaloxime reagent. Independent chemical synthesis confirms the nickel-containing product as the cation, [(triphos)NiMe] + . These studies provide small molecule precedent for a Ni(0) nucleophile during acetyl coenzyme A synthase (ACS) biocatalysis. That the corresponding (triphos)NiCO is not a substrate for the reaction provides a chemical-based rationale for ordered binding of methyl followed by CO.
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Eckert et al. (2007) studied this question.
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