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The phosphorus\u2010containing analogues of triazenes are underexplored but offer great potential as flexible and small bite\u2010angle ligands. This manuscript explores the synthesis and characterisation of a family of air\u2010stable azophosphine\u2010borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. 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