Synthesis, Structure, and Catalysis of Palladium Complexes Bearing a Group 13 Metalloligand: Remarkable Effect of an Aluminum-Metalloligand in Hydrosilylation of CO2

Efficient synthesis and catalysis of a series of palladium complexes having a group 13 metalloligand (Al, Ga, In) are reported utilizing 6,6″-bis­(phosphino)­terpyridine as a new scaffold for Pd–E bonds (E = Al, Ga, In). Systematic investigation revealed unique characteristics of the Al-metalloligand in both structure and reactivity, which exhibited the highest catalytic activity for hydrosilylation of CO2 ever reported (TOF = 19 300 h–1). This study demonstrated fine-tuning of catalyst activity by the precisely designed metalloligand is a promising approach for new catalyst development in synthetic organometallic chemistry.