P-Amino-cyclopentadienylidene-phosphoranes versus P-cyclopentadienyl-iminophosphoranes—tautomeric protic forms of a new bidentate CpPNligand system
作者:Alex R. Petrov、Konstantin A. Rufanov、Burkhard Ziemer、Petra Neubauer、Vasily V. Kotov、Jörg Sundermeyer
DOI:10.1039/b710419g
日期:——
series of new P-amino-cyclopentadienylidene-phosphoranes 2-6 was synthesized by reactions of P1-P3 with 1-AdN3 (2-4) and DipN3 (5,6). In contrast, P-cyclopentadienyl-iminophosphoranes 1 and 7 were obtained as predominant tautomers by reaction of less CH-acidic P3 with less N-basic Me3SiN3 and DipN3. Both tautomers are protonated forms of ambident, potentially chelating constrained-geometry ligands. The
环戊二烯基膦C5H5-PMe2(P1),C5H5-PPh2(P2)和C5Me4H-PMe2(P3)的Staudinger反应与叠氮化物Me3SiN3、1-AdN3(Ad = 1-金刚烷基)和DipN3(Dip = 2,6 -二异丙基苯基)已被研究。产物的性质取决于C5环上磷和氮原子上的取代基:通过P1-P3与1-AdN3(2- 4)和DipN3(5,6)。相反,通过较少的CH-酸性P3与较少的N-碱性Me3SiN3和DipN3的反应,获得了作为主要互变异构体的P-环戊二烯基-亚氨基正膦酸酯。两种互变异构体都是环境可能潜在螯合的约束几何配体的质子化形式。此“ CpPN”配体家族的三个成员(3、4和6)的分子结构