Cooperativity in bond activation chemistry and catalysis on germanium and tin based platforms.

Abstract

Cooperativity between two main-group elements or between a main-group element and a transition metal centre has achieved significant feats over the last decade, a feature widely known in metalloenzymes and transition metal catalysis. Cooperative and synergic effects capitalize on the orbital modalities at the two sites for multi-site activations of small molecules. In main-group chemistry research, most of the pioneering examples of cooperativity are based on those involving the heavier group 14 elements. In this review, we discuss cooperative interactions in representative examples derived from combining two elements (Ge or Sn) having bonds between them (homodinuclear or heterodinuclear with a p-block element) or placed in proximity without having a bond between them. Selective examples where the heterodinuclear systems consist of either Ge or Sn combined with a transition metal centre for multi-site activations are discussed. In this review, we also cover the prospects of element-ligand cooperativity, with particular emphasis on the redox-active ligands. The mechanisms by which bond activations occur across the dinuclear structures are discussed along with critical evaluations. We close by providing our viewpoints to address the forward-looking directions in the field of main-group cooperative catalysis. We hope that this review portrays a future landscape of opportunities within our grasp for designing efficient catalysts and the discovery of new catalytic transformations.

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