Vertical and relaxed structures of a reactive organosilane radical cation from CW and transient resonance Raman spectra

A reactive organosilane radical cation derived from CW and transient resonance Raman spectra features relaxed and vertical structures. Two p-methoxybenzyltrialkylsilanes are obtained both as their radical cations and as their neutral charge-transfer derivatives with tetracyanoethylene in steady-state cw experiments using two-color pump-probe transient measurements. The ground-state charge-transfer resonant spectra show intensity predominantly in phenyl-localized modes, an indication that vertical excitation to the contact ion-pair state has little involvement of the bond that undergoes subsequent nucleophile-assisted cleavage in the separated radical cation.