Adducts of Cyclodiphosph(V)azenes: Synthesis and Structure

The reaction of Ph 2 PCl and PhPCl 2 with bis(trimethylsilyl)sulfur diimide in the presence of GaCl 3 and AlCl 3 yields diadducts of the corresponding cyclodiphosph(V)azene: [Ph 2 PN] 2 ·(GaCl 3 ) 2 ( 1 ), [Ph 2 PN] 2 ·(AlCl 3 ) 2 ( 2 ), and [Ph(Cl)PN] 2 ·(AlCl 3 ) 2 ( 3 ). This reaction is triggered by Lewis acids, which catalyse the (CH 3 ) 3 Si‐Cl and S 8 elimination. The structures of 1· 2 CH 2 Cl 2 , 2· 2 CH 2 Cl 2 and 3 were determined by single crystal X‐ray studies ( 1 : triclinic, $P{\bar 1}$ , a = 9.679(2) Å, b = 9.863(2) Å, c = 11.366(2) Å, α = 113.55(3)°; β = 99.59(3)°; γ = 106.67(3)°; V = 902.8(3) Å 3 , Z = 1; 2 : triclinic, $P{\bar 1}$ , a = 9.639(2) Å, b = 9.804(2) Å, c = 11.321(2) Å, α = 113.71(3)°; β = 99.44(3)°; γ = 106.70(3)°; V = 889.3(3) Å 3 , Z = 1; 3 : orthorhombic, Pbca , a = 14.853(3) Å, b = 9.261(2) Å, c = 16.631(3) Å, V = 2287.7(8) Å 3 , Z = 4.