Monomeric phosphinoboranes

•The developments in the chemistry of R2PBR′2R2PBR′2 over the last 20 years.•Distinction between phosphinoboranes and borylphosphine.•Preparation of R2PBR′2R2PBR′2 and their reactions with H2, amine–boranes, chalcogens, Me3NO and unsaturated organics.•κ1 (P) and η2 (PB) coordination to transition metals.•Borylphosphines as ligands for homogeneous catalysis.

The key developments in the chemistry of R2PBR′2R2PBR′2 over the last 20 years are reviewed. The categorization of phosphinoboranes as R2PBR′2R2PBR′2 species and borylphosphines as R2PBR′2R2PBR′2 species is suggested based on an analysis of the literature X-ray crystal structures. The chemistry of derivatives of the simplest borylphosphine H2PBH2 is discussed. Six methods of preparation of R2PBR′2R2PBR′2 are presented along with the reactions of the products with H2, amine–boranes, elemental chalcogens, Me3NO and compounds featuring CO, CC and CN functionalities. The two modes of coordination of R2PBR′2R2PBR′2 to transition metals, κ1 (P) and η2 (PB), are covered, along with the applications of borylphosphine complexes in homogeneous catalysis.

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