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

(ClImDipp)P-P(Dipp)˙ (1˙), a rare example of a neutral, mixed substituted diphosphene radical, has been prepared by reduction of (ClImDipp)PP(Dipp)[OTf] (2[OTf]) and (ClImDipp)PP(Cl)(Dipp) (3) with cobaltocene (CoCp2) (ClImDipp = 4,5-dichloro-1,3-bis(1,3-diisopropylphenyl)-imidazol-2-yl, Dipp = 2,6-diisopropylphenyl). Radical compound 1˙ readily activates white phosphorus (P4), resulting in the formation of an intriguing octaphosphane butterfly compound P8(ClImDipp)2(Dipp)2 (4).