We designed a new P,O-type hemilabile ligand, <i>N</i>-ditosyl bicyclic bridgehead phosphorus triamide. Two different atoms coordinate to transition metal, thus generating several catalytic features. Firstly, π-acceptor ability of P atom has been increased by its geometric constraint making the transition metal electronically poor. Secondly, the donor O atom weekly coordinates to the transition metal. This week coordination can be dissociated when substrates access to the metal center providing vacant site. Based on these ligand properties, the new ligand has been applied to Pd-catalyzed hydrosilylation. Interestingly, a challenging substrates combination for Pd-catalyzed hydrosilylation, unactivated alkenes and tertiary alkylsilanes, can be achieved by using the new ligand on the catalysis. In addition, the efficiency of new hemilabile ligand on Pd-catalyzed hydrosilylation has been demonstrated by DFT calculation method. Furthermore, the new ligand has been also applied to Pd-catalyzed hydrosilylation of 1-phenylbutadiene. Interestingly, the catalytic system of new ligand provides 1,4-hydrosilylation product, while other Pd-catalysis provides 1,2-hydrosilylation. We expect that the interesting characteristic of new ligand makes different tendency to general Pd catalysis.

Design of new hemilabile hybrid P,O-type ligand promoting Pd-catalyzed hydrosilylation of unactivated alkenes

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.