Chromium tricarbonyl complex of phosphaalkene: Crystal structure and electrochemistry of the Cr(CO)3 complex of PhC(H)PMes*, EPR and DFT studies of its radical anion

Article abstract of DOI:10.1016/j.jorganchem.2005.08.045

We report the synthesis, crystal structure and electrochemical behaviour of a complex in which the Ph group of the phosphaalkene PhC(H)PMes* (Mes*: 2,4,6-tri-tert-butylphenyl) is coordinated to a chromium tricarbonyl group. The EPR spectra resulting from electrochemical and chemical reductions are described and the experimental g and hyperfine tensors ( ³¹P)T, as determined from the EPR data, are compared with those predicted by DFT calculations for the radical anion (Cr(CO)₃, PhC(H)PMes)^-. The structural changes caused by the addition of an electron to the neutral complex are described, together with an estimation of the contribution of Cr(CO)₃ to the stabilization of the radical anion.