Alkoxycarbonyl Groups in Metalloesters Showing Oxocarbenium‐like Structure and Alkylating Reactivity

In contrast to the well‐documented acylating reactivity, the alkylating reactivity of the alkoxycarbonyl group, as signified by its oxocarbenium‐like resonance structure, remains almost unexplored. Herein, the first series of Co/Ni dinuclear metalloesters exhibiting the novel oxocarbenium‐like alkoxycarbonyl groups were synthesized and characterized. In these deformed alkoxycarbonyl groups, the C carbonyl −O alkoxyl bonds were contracted to 1.177(11)~1.191(9) Å with the elongations of the C carbonyl =O carbonyl bonds to 1.368(13)~1.441(9) Å. Meanwhile, the O−C alkyl bonds were also elongated to 1.522(11) ~1.607(15) Å, and were by far the longest O−C alkyl bonds reported for alkoxycarbonyl groups. As triggered by the long O−C alkyl distances, the alkylating reactivity of the oxocarbenium‐like methoxycarbonyl group towards a series of C/N/O‐nucleophiles via the rare B AL 2 mechanism at ambient conditions was examined. Furthermore, the homo‐etherifications of alcohols mediated by the Co/Ni dinuclear metalloesters were investigated. The yields followed the trend ethanol≫ n ‐propanol≫ n ‐butanol ≈ n ‐pentanol, that closely related to the structure features of the alkoxycarbonyl groups in corresponding metalloesters: while the ethoxycarbonyl group showed the reactive oxocarbenium‐like framework, the n ‐propoxycarbonyl group displayed the dioxocarbenium‐like skeleton with a shorter O−C alkyl bond; In comparison, the classical frameworks with unactivated alkyl moieties were observed for n ‐butoxycarbonyl and n ‐pentoxycarbonyl groups.