In the past few decades, main group-based catalysts have attracted increasing attention as an alternative approach to overcome the most prevailing issues of transition metal catalysts such as high cost, toxicity, and low abundance. Among these main group-based catalysts, phosphorous compounds have shown a variety of example of bond activation transformations due to the strong nucleophilicity from their congener species. To the contrary, unique electron deficient boron-based clusters have the tendency to accept two electrons reversibly due to their electron deficiency. In this study, we have utilized a combination of the electron donor ability of the phosphine groups with the electron acceptor ability of the <i>ortho</i>-carborane cluster for synergistic molecular reactivity. The unusual steric and electronic properties of this cluster have demonstrated strong bond activation analogous to transition metal-based bond activation such as oxidative addition and reductive elimination. Herein, metal-free activation of small molecules by the carboranyl phosphines will be presented.

Metal-free reactivity of carboranyl phosphines

ACS Fall 2021

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