Boron Polycation Supported by Cyclic Bis(carbodiphosphorane)

A novel cyclic bis(carbodiphosphorane) ligand was prepared and investigated in coordination with group 13 elements, B, Al, and Ga. Al and Ga afforded dinuclear adduct where two metal centers were bridged by the bis(carbodiphosphorane) ligand. In contrast, the reaction with boron trichloride afforded a monomeric dicationic three-coordinate boron species composed of one boron moieties and one ligand. The structures of these products were determined by X-ray crystallography. In the dicationic boron compound, the sterically constrained cyclic structure enforced the boron center to acquire strained trigonal geometry with wide C-B-C angle of 140°. Furthermore, theoretical investigation with DFT and NBO suggested a significant contribution of tricationic two-coordinate boron resonance structure supported by two CDP ligands.