Solution Photophysics, One-Electron Photooxidation, and Photoinitiated Two-Electron Oxidation of Molybdenum(III) Complexes

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Several six-coordinate Mo(III) complexes phosphoresce and undergo photooxidation in room-temperature solution. The phosphorescence of (Me3[9]aneN3)MoX3 (Me3[9]aneN3 = 1,4,7-trimethyl-l,4,7-triazacyclononane) in CH3-CN at room temperature occurs with the following maxima, lifetimes, and quantum yields: X = Cl, 1120 nm, 1.0 μs, and 6.1 × 10-5; X = Br, 1130 nm, 0.80 μs, and 9.6 × 10-5; and X = I, 1160 nm, 0.40 μs, and 1.2 × 10-4, respectively. The phosphorescences are assigned to the {2Eg, 2T1g} → 4A2g transition. Solutions of HB(Me2pz)3MoIIICl3- Me2pzH = 3,5-dimethylpyrazole) in CH3CN, and solid MoCl3(py)3 and (Me3[9]aneN3)-WCl3, also phosphoresce. (Me3[9]aneN3)MoX3 (X = Cl, Br, I) complexes undergo reversible one-electron photooxidation upon irradiation in the presence of acceptors such as TCNE and chloranil. (Me3[9]aneN3)MoX3 (X = Br, I only) are photooxidized irreversibly to [(Me3[9]aneN3)MoIVX3]+ by C(NO2)4 in CH3CN. In CH3-CN-H2O (1:1 v/v), photoinitiated two-electron oxidation occurs: the primary photoproduct is Mo(IV), which disproportionates spontaneously to form [(Me3[9]aneN3)MovOX2]+.

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Inorganic Chemistry

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