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 [iBu(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.