A neutral diphosphene radical: synthesis, electronic structure and white phosphorus activation.

( Cl Im Dipp )P-P(Dipp)˙ (1˙), a rare example of a neutral, mixed substituted diphosphene radical, has been prepared by reduction of ( Cl Im Dipp )PP(Dipp)[OTf] (2[OTf]) and ( Cl Im Dipp )PP(Cl)(Dipp) (3) with cobaltocene (CoCp 2 ) ( Cl Im Dipp = 4,5-dichloro-1,3-bis(1,3-diisopropylphenyl)-imidazol-2-yl, Dipp = 2,6-diisopropylphenyl). Radical compound 1˙ readily activates white phosphorus (P 4 ), resulting in the formation of an intriguing octaphosphane butterfly compound P 8 ( Cl Im Dipp ) 2 (Dipp) 2 (4).