Comparison of the LMCT resonance Raman spectra of PdCl2 (PCy3)(2) and PdCl2 (PPh3)(2): effect of the phenyl versus cyclohexyl substituents on the LMCT excited state

Resonance Raman spectra have been obtained at four excitation wavelengths w ithin the A-band ligand to metal charge transfer (LMCT) absorption of trans -dichloro-bis(tricyclo-hexylphosphine) palladium(II) and a resonance Raman intensity analysis was done to elucidate the excited state structure relati ve to the ground state. Comparison of the present results for trans-dichlor obis(tricyclohexylphosphine) palladium(II) with those previously reported f or trans-dichlorobis(triphenylphosphine) palladium(II) shows that the pheny l ligand appears to primarily affect the adjacent P-C vibrational reorganiz ational energy and does not significantly perturb the Pd-Cl or Pd-P vibrati onal reorganizational energies.