Investigations on the reactivity of phosphide KP(iPr)R1 toward chalcogens, heteroallenes and an acyl chloride are reported, revealing the distinct nucleophilicity of the potassium phosphide.
The
synthesis of sterically demanding 2,6-bis(2,4,6-trimethylphenyl)phenyl
(Ter)-stabilized and H-substituted diphosphanes TerHP–PR2 (4a–4c) via conversion of
the phosphide TerPHK (2) with secondary chlorophosphanes
ClPR2 (3a–3c, where R
= iPr, Ph, and tBu, respectively)
is described. The diphosphanes 4a–4c were deprotonated using KH in tetrahydrofuran, selectively yielding
the potassium phosphinophosphides K[TerP–PR2] (5a–5c). These phosphinophosphides are
stable in solution as well as in the solid state and can be further
functionalized via salt-metathesis reactions. Reaction with organosilyl
halides selectively yields the silylated diphosphanes Ter(SiR1
2R2)P–P(iPr)2 (6a and 6b, where R1 = R2 = CH3 and R1 = CH3, R2 = Ph, respectively), whereas conversion with chlorophosphanes
selectively yields the triphosphanes R1
2P–P(Ter)–P(iPr)2 (7a and 7b, where
R = iPr and Ph, respectively).
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.