The role of odd-electron intermediates and in-cage electron transfer in ultrafast photochemical disproportionation reactions in Lewis bases.
نویسندگان
چکیده
Femtosecond visible pump-IR probe studies of Cp2W2(CO)6 in P(OMe)3 and CH2Cl2 have allowed direct observation of a 19-electron intermediate and of disproportionation into CpW(CO)3- and CpW(CO)3P(OMe)3+ on the ultrafast time scale. A new disproportionation mechanism involving in-cage electron transfer between a 19-electron intermediate and a 17-electron radical has been proposed.
منابع مشابه
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)3PR3*by coordination of PR3 with photogenerated 17-electron (17e) radicals CpW(CO)3* is directly observed, an...
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ورودعنوان ژورنال:
- Journal of the American Chemical Society
دوره 126 37 شماره
صفحات -
تاریخ انتشار 2004