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• W3122540443 abstract "Abstract We report a series of mononuclear monooxo Mo(IV) complexes possessing either one or two fully oxidized dithiolene ligands; [MoOCl(R 2 Dt 0 ) 2 ][X], ( 1 and 2 ), and MoO( p ‐SC 6 H 4 Y) 2 (R 2 Dt 0 ), ( 3 and 4 ), (R=Me, i Pr; X=PF 6 , SbF 6 , BF 4 ; Y=H, Cl, F, CF 3 , Me, t Bu, OMe). Either four or two quasi‐reversible ligand‐based redox couples are detected depending upon the number of fully oxidized dithiolene ligands present. The molecular structure of 3 and 4 exhibit a large (47° to 70°) fold angle along the S⋅⋅⋅S vector of the dithione ligand. The UV‐Vis spectra of 3 and 4 exhibit a low energy charge transfer band at ∼540 nm that are red‐shifted ∼200 nm compared to the spectra of 1 and 2 . Density Functional Theory (DFT) calculations show that the low energy charge transfer band of 3 and 4 is heavily influenced by ligand fold angle. Reducing the fold angle decreases the charge transfer energy, and the transition becomes more ligand‐based." @default.
• W3122540443 created "2021-02-01" @default.
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• W3122540443 date "2021-02-03" @default.
• W3122540443 modified "2023-09-23" @default.
• W3122540443 title "The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of Mo ^IV O‐Dithione Complexes" @default.
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• W3122540443 doi "https://doi.org/10.1002/ejic.202001155" @default.
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