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.