White Phosphorus Reduction and Oligomerization by a Potassium Diamidoalumanyl

Abstract Reactions of the potassium alumanyl derivative, [K{Al(SiN Dipp )}] 2 (SiN ={CH SiMe NDipp} ), with white phosphorus result in two electron reduction to provide controlled access species containing (P 4 ) 2− dianion. Two examples have been crystallographically characterized, a monomeric derivative which cation is encapsulated by 18‐crown‐6 (18‐cr‐6) and 1‐dimensional polymeric isolated from diethyl ether solution. Although reactions performed at more elevated temperatures presence additional equivalents P resulted similar outcomes, these conditions also oligomerization, albeit as yet unidentified mechanisms. The structures [{(SiN )AlK(THF) } 6 )] )AlK(toluene) 16 have, thus, characterized interrogated computationally quantum chemical (DFT, QTAIM) methods.