Expanding the scope of bis(catecholato)germane catalysis: hydrosilylation, hydroboration, Friedel-Crafts alkylation and oligomerization.

Various applications of bis(catecholato)germanes in catalysis were examined. The hydrosilylation of benzaldehydes, hydroboration of phenylacetylene derivatives, and Friedel-Crafts alkylation using arylalkenes and either diphenylamine or anisole was achieved. Furthermore, the recently reported oligomerization of α-methylstyrene catalyzed by bis(catecholato)germanes with weak donor ligands was examined further. The formation of a trimer species was observed in DCM. VTNA and Hammett analyses of the oligomerization reaction were conducted and an updated mechanism for bis(catecholato)germane catalysis is proposed.

Selective dimerization of α-methylstyrene by tunable bis(catecholato)germane Lewis acid catalysts.

The synthesis of a variety of bis(catecholato)germanes is reported. The Lewis acidity of the bis(catecholato)germanes was assessed using the experimental Gutmann-Beckett method and computational FIA and GEI methods. The oligomerization of alkenes using bis(catecholato)germanes demonstrates the use of these complexes in catalysis. The use of donor additives in the dimerization of α-methylstyrene resulted in selectivity control comparable to transition metal catalyst systems.