Reaction of Ph2P(8-CH2C9H6N)＝NBut (1) with 2 equiv of AlMe3 in toluene under reflux conditions afforded aluminum iminophosphorano(2-methyl-8-quinolyl)methandiide complex (2). The reaction proceeded via the intermediates of a coordination complex, [(AlMe3){Ph2P-(8-CH2C9H6N)＝NBut}] (3), and then an addition complex (4) of AlMe3 to the carbon-nitrogen double bond of the quinolyl ring of the neutral ligand. The coordination complex was converted to the singly deprotonated complex [(AlMe2){CH(8-C9H6N)(Ph2P＝NBut)}] (5) at 60℃, which further reacted with AlMe3 in toluene under reflux conditions to yield aluminum iminophosphorano (8-quinolyl) methandiide (6). The structures of complexes 2, 4, and 6 were proved by single-crystal X-ray diffraction techniques, and the five-coordinate complexes 3 and 5 were characterized by 27Al NMR spectroscopy.

The lithium complex [HC(PPh2＝NSiMe3)2Li(THF)] (2) prepared by the reaction of BunLi with bis (iminophosphorano) methane reacts with GeCl2·dioxane in different stoichiometric ratios to afford [HC(PPh2＝NSiMe3)2GeCl] (3) and [(Me3SiN＝PPh2)2C＝Ge→Ge＝C(PPh2＝NSiMe3)2] (4), respectively. Bisgermavinylidene 4 can also be obtained by the reaction of 3 with [Ge{N(SiMe3)2}2] or 2. Further reaction of 4 with Me3NO afforded [(μ-N＝Ph2P)(Me3-SiN＝Ph2P)C＝Ge(OSiMe3)]2 (5), and direct reaction of elemental chalcogens (sulfur, selenium, and tellurium) with 4 afforded [(Me3SiN＝PPh2)2C＝Ge(μ-E)]2 [E＝S (6), Se (7), and Te (8)]. X-ray structures of compounds 2-8 have been determined.

Reaction of PhaP(C≡CBut)=NSiMe3 (1) with KP(H)Ph afforded 3-(iminophosphorano)-l-phosphaallyl potassium, [K{P(Ph)C(But)=C(H)P(Ph)a=NSiMe3}(OEta)3] [3·(OEta)3], which was recrystallized from EtaO to give a solvent-free complex, [K{P(Ph)C(But)=C(H)P(Ph)a=N-SiMe3}]∞ (3). Treatment of MeaP(C≡CPh)=NSiMe3 (2) with LiP(R)Ph (R＝H, SiMeaBut) formed 2-(iminop hosp horano)-1-phosp haallyllithium, [Li{P(Ph)C{=C(R)Ph}P(Me)a=NSiMe3}-(THE)n] (R＝H, n＝1.5, 4; R＝SiMeaBut, n＝2, 5), via a hydrogen or SiMeaBut group 1,3-P→C migration. Reaction of 4 or 5 with SnCla in 2:1 ratio in EtaO yielded P, N-chelatingtin(II) complexes [Sn{P(Ph)C{=C(R)Ph}P(Me)a=NSiMe3}a] (R＝H, 6; R＝SiMeaBut, 7). Complex 6 was also obtained by treatment of C1SnN(SiMe3)2 with 1 equiv of 4. X-ray data are provided for 3, 5, and 6. Complex 3 is polymeric in the solid state without coordinated solvent molecules, whereas both crystalline 5 and 6 are monomeric.

Reaction of MP(Ph)SiMe2But(M=Li, K) with an equivalent of PhCN afforded the 1-aza-3-phosphaallyllithium and-potassium complexes [M{P(Ph)C(Ph)NSiMeBut}(L)]2(1,M=THF;2, M=K, L=Et2O), respetively. Exposing 2 in vacuo at room temperature, the solvent-free complex [K{P(Ph)C(Ph)NSiMe2But}] (3) was obtained. Treatment of 1 with SnCl2 in 2:1 ratio funished the homoleptic tin (Ⅱ) comples [Sn{P(Ph)C(Ph)NSiMe2But}2] (4). Compound 1 reacted with an equimolar amount of C1SnN(SiMe3)2 to give [P(Ph)C(Ph)=NsiMe2But}]2 (5) via ligand coupling. Reaction of 3 with PhCN produced [K{P(Ph)C(Ph)NC(Ph)NSiMe2But}](6) by addition of the nitrogen atom to PhCN followed of 3 with PhCN produced [K{P(Ph)C(Ph)NC(Ph)NSiMe2But}] (6) by addition of the nitrogen atom th PhCN followed by a 1,3-N→N' migration of the SiMe2But group. Structures of compounds 1,2,4 and 5 have been determinded bysingle crystal X-ray diffraction techniques. The complexes 1 and 2 are dimeric and 4 is both monomeric, while 5 is the product of ligand coupling with formation of new P-P bond.