Phosphine‐Stabilized Pnictinidenes
Dominik Raiser, Klaus Eichele, Hartmut Schubert, Lars Wesemann
Abstract
Abstract The reaction of the intramolecular germylene‐phosphine Lewis pair (o‐PPh 2 )C 6 H 4 GeAr* ( 1 ) with Group 15 element trichlorides ECl 3 (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds ( o ‐PPh 2 )C 6 H 4 (Ar*)Ge(Cl)ECl 2 ( 2 : E=P, 3 : E=As, 4 : E=Sb) were reduced by using sodium metal or LiHBEt 3 . The molecular structures of the phosphine‐stabilized phosphinidene ( o ‐PPh 2 )C 6 H 4 (Ar*)Ge(Cl)P ( 5 ), arsinidene ( o ‐PPh 2 )C 6 H 4 (Ar*)Ge(Cl)As ( 6 ) and stibinidene ( o ‐PPh 2 )C 6 H 4 (Ar*)Ge(Cl)Sb ( 7 ) are presented; they feature a two‐coordinate low‐valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [( o ‐PPh 2 )C 6 H 4 (Ar*)GeP] [B(C 6 H 3 (CF 3 ) 2 ) 4 ] ( 8 ) was isolated. The 31 P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [ i Bu 2 AlH] 2 , and the product of an Al−H addition to the low‐valent phosphorus atom ( o ‐PPh 2 )C 6 H 4 (Ar*)Ge(H)P(H)Al(C 4 H 9 ) 2 ( 9 ) was characterized.