765308-04-1Relevant academic research and scientific papers
Syntheses, Structures, Bonding and Photoelectron Spectra of "Push-Pull"-Substituted P-[2,6-Bis(trifluoromethyl)phenyl]-?2λ3-iminophosphanes
Miqueu, Karinne,Sotiropoulos, Jean-Marc,Pfister-Guillouzo, Genevieve,Rudzevich, Valentyn L.,Gornitzka, Heinz,Lavallo, Vincent,Romanenko, Vadim D.
, p. 2289 - 2300 (2004)
?2λ3-"Push-pull" iminophosphanes 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 ArfP=NNMe2 (6) in order to determine the electronic effect of the Arf substituent and the influence of the donor group R on the stability of the monomeric species. A comparison of the theoretical results and UV photoelectron spectroscopy data for the iminophosphanes 4 and 6 is presented. Theoretical and experimental data suggest that for all iminophosphanes under investigation the ?-system of the Arf group is almost orthogonal to the ?P=N system, preventing any stabilizing interaction between the ?P=N and ?*b1(aryl) orbitals previously observed for the ArfPH- anion. Here, the Arf substituent effect is mainly steric.
