Syntheses, Structures, Bonding and Photoelectron Spectra of “Push‐Pull”‐Substituted
<i>P</i>
‐[2,6‐Bis(trifluoromethyl)phenyl]‐σ
<sup>2</sup>
λ
<sup>3</sup>
‐iminophosphanes
作者:Karinne Miqueu、Jean‐Marc Sotiropoulos、Genevieve Pfister‐Guillouzo、Valentyn L. Rudzevich、Heinz Gornitzka、Vincent Lavallo、Vadim D. Romanenko
DOI:10.1002/ejic.200300823
日期:2004.6
Arf−P=N−R, bearing an electron-acceptor substituent at phosphorus [Arf = 2,6-bis(trifluoromethyl)phenyl] and a donor group at nitrogen (R = tBu, NMe2), have been synthesized and characterized by NMR spectroscopy and X-ray analysis. Density functional calculations [B3LYP/6-311G(d,p)] have been carried out on different iminophosphanes: HP=NH (1), ArfP=NH (2), ArfP=NSiMe3 (3), ArfP=NtBu (4), HP=NNMe2 (5) and
σ2λ3-“推拉”亚氨基膦Arf-P=NR,在磷[Arf = 2,6-双(三氟甲基)苯基]处带有一个电子受体取代基,在氮处带有一个供体基团(R = tBu,NMe2) , 已合成并通过核磁共振光谱和 X 射线分析表征。已经对不同的亚氨基膦进行了密度泛函计算 [B3LYP/6-311G(d,p)]:HP=NH (1), ArfP=NH (2), ArfP=NSiMe3 (3), ArfP=NtBu (4) , HP=NNMe2 (5) 和 ArfP=NNMe2 (6) 以确定 Arf 取代基的电子效应和供体基团 R 对单体物种稳定性的影响。比较了亚氨基膦 4 和 6 的理论结果和紫外光电子能谱数据。理论和实验数据表明,对于所有正在研究的亚氨基膦,Arf 基团的 π 系统几乎与 πP=N 系统正交,从而防止了 πP=N 和先前观察到的 π*b1(芳基)轨道之间的任何稳定相互作用ArfPH− 阴离子。这里,Arf