Isolable Diaminophosphide Boranes

Metalation of secondary diaminophosphine boranes by alkali metal amides provides a robust and selective access route to a range of metal diaminophosphide boranes M[(R(2)N)(2)P(BH(3))] (M=Li, Na, K; R=alkyl, aryl) with acyclic or heterocyclic molecular backbones, whereas reduction of a chlorodiaminophosphine borane gave less satisfactory results. The metalated species were characterized in situ by NMR spectroscopy and in two cases isolated as crystalline solids. Single‐crystal XRD studies revealed the presence of salt‐like structures with strongly interacting ions. Synthetic applications of K[(R(2)N)(2)P(BH(3))] were studied in reactions with a 1,2‐dichlorodisilane and CS(2), which afforded either mono‐ or difunctional phosphine boranes with a rare combination of electronegative amino and electropositive functional disilanyl groups on phosphorus, or a phosphinodithioformate. Spectroscopic studies gave a first hint that removal of the borane fragment may be feasible.