Synthesis, Redox and Spectroscopic Properties of Pterin of Molybdenum Cofactors.

Pterins are bicyclic heterocycles that are found widely across Nature and are involved in a variety of biological functions. Notably, pterins are found at the core of molybdenum cofactor (Moco) containing enzymes in the molybdopterin (MPT) ligand that coordinates molybdenum and facilitates cofactor activity. Pterins are diverse and can be widely functionalized to tune their properties.

Interligand communication in a metal mediated LL'CT system - a case study.

A series of oxo-Mo(iv) complexes, [MoO(Dt)(Dt)] (where Dt = benzene-1,2-dithiol (bdt), toluene-3,4-dithiol (tdt), quinoxaline-2,3-dithiol (qdt), or 3,6-dichloro-benzene-1,2-dithiol (bdtCl); Dt = ,'-dimethylpiperazine-2,3-dithione (MeDt) or ,'-diisopropylpiperazine-2,3-dithione ( PrDt)), possessing a fully oxidized and a fully reduced dithiolene ligand have been synthesized and characterized. The assigned oxidation states of coordinated dithiolene ligands are supported with spectral and crystallographic data. The molecular structure of [MoO(tdt)( PrDt)] () demonstrates a large ligand fold angle of 62.

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

Two sets of Fe dithione complexes [Fe( PrDt)][PF] ([1][PF]), [Fe(MeDt)][PF] ([2][PF]), and [Fe( PrDt)][PF] ([3][PF]), [Fe(MeDt)][PF] ([4][PF]), and compound [Fe( PrDt)][FeCl][PF] ([3][FeCl][PF]) were synthesized from ,'-diisopropyl piperazine-2,3-dithione ( PrDt) and ,'-dimethyl piperazine-2,3-dithione (MeDt) ligands. Complexes [1][PF]-[4][PF] have been characterized by NMR, IR, and UV-visible spectroscopies, and by electrochemistry. The molecular structures of [2][PF] and [3][FeCl][PF] have been determined by X-ray crystallography.

Dithione, the antipodal redox partner of ene-1,2-dithiol ligands and their metal complexes.

Defining the oxidation state of the central atom in a coordination compound is fundamental in understanding the electronic structure and provides a starting point for elucidating molecular properties. The presence of non-innocent ligand(s) can obscure the oxidation state of the central atom as the ligand contribution to the electronic structure is difficult to ascertain. Redox-active ligands, such as dithiolene ligands, are well known non-innocent ligands that can exist in both a fully reduced (Dt) and fully oxidized (Dt) states.