Experimental Evidence for p Ka-Driven Asynchronicity in C-H Activation by a Terminal Co(III)-Oxo Complex

Abstract

C-H activation by transition metal oxo complexes is a fundamental reaction in oxidative chemistry carried out by both biological and synthetic systems. This centrality has motivated efforts to understand the patterns and mechanisms of such reactivity. We have therefore thoroughly examined the C-H activation reactivity of the recently synthesized and characterized late transition metal oxo complex PhB ( ^tBuIm)₃Co^IIIO. Precise values for the p K_a and BDFE_O-H of the conjugates of this complex have been experimentally determined and provide insight into the observed reactivity. The activation parameters for the reaction between this complex and 9,10-dihydroanthracene have also been measured and compared to previous literature examples. Evaluation of the rates of reaction of PhB( ^tBuIm)₃Co^IIIO with a variety of hydrogen atom donors demonstrates that the reactivity of this complex is dependent on the p K_a of the substrate of interest rather than the BDE_C-H. This observation runs counter to the commonly cited reactivity paradigm for many other transition metal oxo complexes. Experimental and computational analysis of C-H activation reactions by PhB( ^tBuIm)₃Co^IIIO reveals that the transition state for these processes contains significant proton transfer character. Nevertheless, additional experiments strongly suggest that the reaction does not occur via a stepwise process, leading to the conclusion that C-H activation by this Co^III-oxo complex proceeds by a p K_a-driven "asynchronous" concerted mechanism. This result supports a new pattern of reactivity that may be applicable to other systems and could result in alternative selectivity for C-H activation reactions mediated by transition metal oxo complexes.