Synthesis of Stable Potassium Phosphinophosphides and Reaction with Organosilyl Halides and Chlorophosphanes.

The synthesis of sterically demanding 2,6-bis(2,4,6-trimethylphenyl)phenyl (Ter)-stabilized and H-substituted diphosphanes TerHP-PR 2 ( 4a - 4c ) via conversion of the phosphide TerPHK ( 2 ) with secondary chlorophosphanes ClPR 2 ( 3a - 3c , where R = i Pr, Ph, and t Bu, respectively) is described. The diphosphanes 4a - 4c were deprotonated using KH in tetrahydrofuran, selectively yielding the potassium phosphinophosphides K[TerP-PR 2 ] ( 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(SiR 1 2 R 2 )P-P( i Pr) 2 ( 6a and 6b , where R 1 = R 2 = CH 3 and R 1 = CH 3 , R 2 = Ph, respectively), whereas conversion with chlorophosphanes selectively yields the triphosphanes R 1 2 P-P(Ter)-P( i Pr) 2 ( 7a and 7b , where R = i Pr and Ph, respectively).