The reactivity of the terminal zirconium(iv) oxo complex, O[triple bond, length as m-dash]Zr(MesNPPr)CoCN Bu (), is explored, revealing unique redox activity imparted by the pendent redox active cobalt(i) center. Oxo complex can be chemically reduced using Na/Hg or PhC to afford the Zr/Co complexes [(μ-Na)OZr(MesNPPr)CoCN Bu] () and PhCOZr(MesNPPr)CoCN Bu (), respectively. Based on the cyclic voltammogram of , Ph˙ should not be sufficiently reducing to achieve the chemical reduction of , but sufficient driving force for the reaction is provided by the nucleophilicity of the terminal oxo fragment and its affinity to bind PhC. Accordingly, reacts readily with [PhC][BPh] and PhCCl to afford [PhCOZr(MesNPPr)CoCN Bu][BPh] () and PhCOZr(MesNPPr)CoCl (), respectively. The chemical oxidation of is also investigated, revealing that oxidation of is accompanied by immediate hydrogen atom abstraction to afford the hydroxide complex [HOZr(MesNPPr)CoCN Bu] (). Thus it is posited that the transient [OZr(MesNPPr)CoCN Bu] [] cation generated upon oxidation combines the basicity of a nucleophilic early metal oxo fragment with the oxidizing power of the appended cobalt center to facilitate H-atom abstraction.
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| http://dx.doi.org/10.1039/d0sc04229c | DOI Listing |
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