A diphosphene ligand possessing a PP bond and a phosphineborane moiety in its molecule was synthesized. The reaction of the new bidentate diphosphene-phosphineborane ligand with [Rh(cod)]BF provided a cationic diphosphene-rhodium complex with -coordination through the η-PP and η-BH moieties. The complex was applied to the coupling reaction of benzimidazole with cyclohexylallene. The complex also underwent a ligand exchange reaction with N-donor reagents such as -methylpyrrolidine and ,,,-tetramethylethylenediamine. In particular, the addition reaction of pyridine with the rhodium complex provided an equilibrium mixture of the rhodium complex, pyridine, the diphosphene-phosphineborane ligand, and [Rh(pyridine)(cod)]BF.
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