The catalytic activity and selectivity of homogeneous transition metal catalysts are often tuned by changing the structure and electronic properties of the supporting ligands.  In electrophilic transition metal catalysis the presence of donating ligands can decrease the reactivity of the metal, and thus significant work has focused on developing highly electron deficient supporting ligand frameworks. Work in our laboratory focuses on using a second transition metal �ligand� to tune the electronic properties of the catalytically active metal via formation of a metal�metal bonding interaction. Early-late transition metal heterobimetallic complexes could take advantage of this metal�metal interaction to generate catalysts with unprecedented activity and selectivity in electrophilic catalysis. This poster will describe our initial investigations on phosphinoamide based Ti-�M (M = Pt, Pd, Au) heterobimetallic complexes and their ability accelerate transition metal catalyzed reactions.  We have employed both computational and experimental mechanistic investigation to determine the potential of the M�M interaction to lowering transition-state barriers in electrophilic amination reactions. We will also describe early attempts to develop titanium-containing �ligands� capable of conveniently assembling the desired bimetallic interaction in situ to provide readily accessible, highly active electrophilic transition metal catalysts.

Heterobimetallic phosphonamide-based Ti-M complexes as catalysts in electrophilic transition metal catalysis

248th National Meeting (2014)

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