Caractérisation de complexes de Vanadium (III) présentant une géométrie de bipyramide-trigonale

Matrix Isolation and Theoretical Study of the Photochemical Reaction of PH3 with OVCl3 and CrCl2O2

“…VCl 3 (or Cl 2 CrO), the second product of this reaction, is known to be a strong Lewis acid, − forming complexes with a number of electron donors, including (CH 3 ) 3 N and (CH 3 ) 3 P. While little is known about the coordination chemistry of H 3 PO, (CH 3 ) 3 PO is a strong Lewis base, and coordinates through the oxygen atom to Lewis acids. − In doing so, red-shifts between 70 and 110 cm -1 have been reported in complexes to transition metal centers. − This provides a rationale for the 100+ cm -1 shift observed here, and the very slight differences in the spectra for the OVCl 3 + PH 3 and CrCl 2 O 2 + PH 3 systems, since VCl 3 is the Lewis acid partner in the former case, and Cl 2 CrO in the latter case. This also accounts for the differences between 400 and 500 cm -1 , where the V−Cl and Cr−Cl stretching modes occur.…”