Easy Access to Phosphine-Borane Building Blocks.

In this paper, we highlight the synthesis of a variety of primary phosphine-boranes (RPH2 ⋅BH3 ) from the corresponding dichlorophosphines, simply by using Li[BH4 ] as reductant and provider of the BH3 protecting group. The method offers facile access not only to alkyl- and arylphosphine-boranes, but also to aminophosphine-boranes (R2 NPH2 ⋅BH3 ) that are convenient building blocks but without the protecting BH3 moiety thermally labile and notoriously difficult to handle. The borane-protected primary phosphines can be doubly deprotonated using n-butyllithium to provide soluble phosphanediides Li2 [RP⋅BH3 ] of which the phenyl-derivative Li2 [PhP⋅BH3 ] was structurally characterized in the solid state.