Hypochlorite is known to oxidatively degrade the corrin ring of cobalamin. Here, transient reaction intermediates are described in the reaction of aqua as well as of cyano-cobalamin with hypochlorite, using stopped-flow UV–vis kinetics. For aqua-cobalamin, the intermediate is assigned as arising from substitution of the aqua ligand with hypochlorite. For cyano-cobalamin, the intermediate is proposed to arise from substitution of the benzimidazole ligand trans to the cyanide. In both cases, the intermediates would feature a new Co(III)-OCl⁻bond—which is also supported by density functional theory (DFT) calculations.

Graphical abstract

中文翻译：

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氰基和水钴胺与次氯酸盐的加合物

已知次氯酸盐会氧化降解钴胺素的咕啉环。在这里，使用停流紫外可见动力学描述了水以及氰基钴胺素与次氯酸盐反应中的瞬态反应中间体。对于水钴胺素，该中间体被指定为由次氯酸盐取代水配体而产生。对于氰基钴胺素，建议中间体由苯并咪唑配体反式取代氰化物而产生。在这两种情况下，中间体都会具有新的 Co(III)-OCl ^-键，这也得到了密度泛函理论 (DFT) 计算的支持。

图形概要