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[(R2N)(2)P(BH3)] (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[(R2N)(2)P(BH3)] were studied in reactions with a 1,2-dichlorodisilane and CS2, 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.Peer reviewe