19-Electron intermediates and cage-effects in the photochemical disproportionation of [CpW(CO)3]2 with Lewis bases

The role of 19-electron intermediates in the photochemical disproportionation of [CpW(CO)(3)](2) (Cp = C5H5) with Lewis bases (PR3; R = OMe, Bu, Ph) is investigated on the ultrafast time scale using femtosecond VIS-pump, IR-probe spectroscopy. Formation of a 19-electron (19e) species CpW(CO)(3)PR3 center dot by coordination of PR3 with photogenerated 17-electron (17e) radicals CpW(CO)(3)(center dot) is directly observed, and equilibrium is established between the 17e radicals and the 19e intermediates favoring 19e intermediates in the order: Bu > OMe >> Ph. Steric effects dominate the 17e/19e equilibrium when the cone-angle of the Lewis base exceeds a certain limiting value (between 132 degrees and 145 degrees), but below this value electronic properties of the Lewis base control the 17e/19e dynamics. Disproportionation occurs in less than 200 picoseconds by electron transfer between a solvent caged 17e radical and 19e, highly reducing species. The rate and extent of ultrafast disproportionation depends on both the identity and concentration of the Lewis base. In low concentrations of PR3 (typically 1-2 M or less) or with Lewis bases whose equilibrium heavily favors 17e radicals (e.g., PPh3), disproportionation is rate-limited by breakdown of the solvent cage. Density functional theory calculations on vibrational frequencies and charge distributions of the various complexes support the experimental results.