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Characterization of transient species and products in photochemical reactions of Re(dmb)(CO)3 Et with and without CO2

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Transient FT-IR spectra of fac-Re(dmb)(CO)3(Et) after laser excitation (355 nm) were investigated in THF under Ar and CO2 atmospheres. The CO stretching bands of Re(dmb)(CO)3(THF) grow (2008 and 1897 cm−1) and those of Re(dmb)(CO)3(Et) bleach (1987 and 1875 cm−1) at times < 1 μs, consistent with clean cleavage of the Re–Et bond. Under a CO2 atmosphere, the long-lived radical (τ > 100 ms) converts slowly to the formato complex, Re(dmb)(CO)3(OC(O)H) (2020, 1916, 1873 and 1630 cm−1). When the solvent is slightly wet, the bicarbonato complex, Re(dmb)(CO)3(OC(O)OH), is also observed after photolysis under CO2.


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