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

Thesynthesis of sterically demanding 2,6-bis-(2,4,6-trimethylphenyl)-phenyl(Ter)-stabilized and H-substituted diphosphanes TerHP-PR2 (4a-4c) via conversion ofthe phosphide TerPHK (2) with secondary chlorophosphanesClPR(2) (3a-3c, where R= iPr, Ph, and tBu, respectively)is described. The diphosphanes 4a-4c were deprotonated using KH in tetrahydrofuran, selectively yieldingthe potassium phosphinophosphides K-[TerP-PR2] (5a-5c). These phosphinophosphides arestable in solution as well as in the solid state and can be furtherfunctionalized via salt-metathesis reactions. Reaction with organosilylhalides selectively yields the silylated diphosphanes Ter-(SiR1 R-2(2))-P-P-(iPr)(2) (6a and 6b, where R-1 = R-2 = CH3 and R-1 = CH3, R-2 = Ph, respectively), whereas conversion with chlorophosphanesselectively yields the triphosphanes R-1 P-2-P-(Ter)-P-(iPr)(2) (7a and 7b, whereR = iPr and Ph, respectively). Bulky H-substituted diphosphanes are synthesized and subsequentlydeprotonated using KH in tetrahydrofuran. The resulting potassiumphosphinophosphides are stable in solution and in the solid stateand can be used to selectively synthesize Si-substituted diphosphanesor triphosphanes.

Automated summary

The synthesis of sterically demanding 2,6-bis-(2,4,6-trimethylphenyl)-phenyl (Ter)-stabilized and H-substituted diphosphanes via conversion of phosphide with secondary chlorophosphanes is described. The resulting potassium phosphinophosphides can be further functionalized and selectively used to synthesize Si-substituted diphosphanes or triphosphanes.