Lithium, potassium, and tin(II) complexes of novel 3-(Iminophosphorano)-l-phosphaallyl and 2-(Iminophosphorano)-l-phosphaallyl ligands

摘要

Reaction of Ph2P(Cequivalent toCBu(t)=NSiMe3 (1) with KP(H)Ph afforded 3-(iminophosphorano)-1-phosphaallyl potassium, [K{P(Ph)C(Bu-t)=C(H)P(Ph)(2) = NSiMe3}(OEt2)(3)] [3-(OEt2)(3)], which was recrystallized from Et2O to give a solvent-free complex, [K{P(Ph)C(Bu-t)=C(H)P(Ph)(2)=NSiMe3}](infinity) (3). Treatment of Me2P(Cequivalent toCPh)=NSiMe3 (2) with LiP(R)Ph (R = H, SiMe2But) formed 2-(iminophosphorano)-1-phosphaallyllithium, [Li{P(Ph)C{=C(R)Ph}P(Me)(2)=NSiMe3}-(THF)(n)] (R = H, n = 1.5, 4; R = SiMe2But, n = 2, 5), via a hydrogen or SiMe2But group 1,3-P --> C migration. Reaction of 4 or 5 with SnCl2 in 2:1 ratio in Et2O yielded P, N-chelating tin(II) complexes [Sn{P(Ph)C{=C(R)Ph}P(Me)(2)=SiMe3}(2)] (R = H, 6; R = SiMe2But, 7). Complex 6 was also obtained by treatment of ClSnN(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. [References: 88]