Metal-ligand cooperativity has become a frequently exploited strategy in many catalytic and stoichiometric transformations. While cooperation between an electron-rich transition metal and a two-electron acceptor (“Z-type ligand”) represents an increasingly leveraged subset of cooperative reactivity, the scope of known reactions occurring across such a reverse-dative bond has remained quite limited. In this talk, we will detail the expansive reactivity profile of the platinum (boryl)iminomethane (BIM) complex Pt(κ2-N,B-Cy2BIM)(CNArDipp2), which contains a reverse-dative Pt→B interaction. Bond activations across this linkage can be described as either oxidative addition or oxidative insertion, the latter of which represents a new reactivity paradigm for metal→borane complexes. Remarkably, these insertions can be coupled with C-N bond formation to effect substrate functionalization and product release from the Pt center. A combination of experiment and theory are used to gain insight into the mechanisms of these transformations.

Breaking and forming bonds through metal-borane cooperation

254th National Meeting (2017)

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