Syntheses, spectroscopic, redox, and structural properties of homoleptic Iron(III/II) dithione complexes

We report a series of mononuclear monooxo Mo(IV) complexes possessing either one or two fully oxidized dithiolene ligands; [MoOCl(R2Dt0)2][X], (1 and 2), and MoO(p‐SC6H4Y)2(R2Dt0), (3 and 4), (R=Me, iPr; X=PF6, SbF6, BF4; Y=H, Cl, F, CF3, Me, tBu, 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.

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The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of Mo^IVO‐Dithione Complexes

Dille

Colston

Mogesa

et al. 2021

Eur J Inorg Chem

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Syntheses, spectroscopic, redox, and structural properties of homoleptic Iron(III/II) dithione complexes

Abstract: Two sets of FeIII/II complexes, synthesized from N,N′-diisopropyl piperazine-2,3-dithione (iPr2Dt0) and N,N′-dimethyl piperazine-2,3-dithione (Me2Dt0) ligands, exhibit electronically asymmetrical ligands with metal–ligand orbital mixing.

Cited by 1 publication

References 63 publications

The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of Mo^IVO‐Dithione Complexes

The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of Mo^IVO‐Dithione Complexes

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Syntheses, spectroscopic, redox, and structural properties of homoleptic Iron(III/II) dithione complexes

Abstract: Two sets of FeIII/II complexes, synthesized from N,N′-diisopropyl piperazine-2,3-dithione (iPr2Dt0) and N,N′-dimethyl piperazine-2,3-dithione (Me2Dt0) ligands, exhibit electronically asymmetrical ligands with metal–ligand orbital mixing.

Cited by 1 publication

References 63 publications

The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of MoIVO‐Dithione Complexes

The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of MoIVO‐Dithione Complexes

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The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of Mo^IVO‐Dithione Complexes

The Impact of Ligand Oxidation State and Fold Angle on the Charge Transfer Processes of Mo^IVO‐Dithione Complexes