The “Dendritic Effect” in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts: Observation of Active-Site Proximity Effects in Atom-Transfer Radical Addition

Abstract

Advantages of homo- and heterogeneous catalysts are united in metallodendritic molecules where nickel-based catalysts are bound to carbosilane dendrimers. The first direct indication of a "dendritic effect" in the redox catalysis behavior is described: variation of the dendrimer support controls the proximity of the Ni(II) centers, which in turn controls catalytic activity. Catalyst deactivation, by means of Ni(III) formation, can be avoided by a larger separation of the Ni(II) centers (see picture).