Synthesis of Heavy Dicyanamide Homologues from Air-Stable Precursors

Abstract

A convenient synthesis of dicyanophosphide and dicyanoarsenide anions is reported. These heavy homologues of the long-known and fundamentally important dicyanamide anion were formed through the nucleophilic displacement of bis(diphenylphosphino)ethane (dppe) from the pnictogen⁺ transfer agents [dppePn][BPh₄ ] (Pn=P, As) by exposure to cyanide salts. The protocol requires three synthetic steps from commercially available materials and the [dppePn][BPh₄ ] salts are remarkably temperature, air, and moisture stable. All products have been fully characterized by spectroscopic methods and by single-crystal X-ray diffraction, and the electronic structures of the DCPn anions have been assessed computationally.

Keywords: cyanides; dicyanoarsenide; dicyanopnictide; homologous compounds; main group chemistry; pnictogens.