Synthesis, electronic structure, and structural characterization of the new, "non-innocent" 4,5-dithio-catecholate ligand, its metal complexes, and their oxidized 4,5-dithio-o-quinone derivatives.

The bifunctional ligand catechol-4,5 dithiol, H(2)Dtcat, has been synthesized, and the structure of the bis Br(-) adduct, (HS)(2)C(6)H(2)(OH)(2).2Ph(4)Br.H(2)O, has been determined.

Reactivity and kinetic studies of (NH4)2(MoS4) in acidic aqueous solution: possible relevance to the angiostatic function of the MoS4(2-) ligand.

Although addition of mineral acids to WS(4)(2-) in water is known to lead to aggregation and formation of various polynuclear thiotungstate anions, acid hydrolysis of the MoS(4)(2-) anion is reported to give mainly MoS(3) or MoS(2) as hydrolysis products. Knowledge of the resulting product(s) from such reactions has implications on the use of tetrathiomolybdate (MoS(4)(2-)) as both a potential anti-tumor drug and for the treatment of Wilson's disease. In this investigation, reaction of HCl with MoS(4)(2-) in water was monitored as a function of time.

Synthesis and reactivity of a new octanuclear iron-sulfur nitrosyl cluster.

The synthesis and spectroscopic properties of (PPN)2[Fe8S6(NO)8] as well as its reactivity toward sulfur are reported.

Dynamics of an [Fe4S4(SPh)4]2- cluster explored via IR, Raman, and nuclear resonance vibrational spectroscopy (NRVS)-analysis using 36S substitution, DFT calculations, and empirical force fields.

We have used four vibrational spectroscopies--FT-IR, FT-Raman, resonance Raman, and 57Fe nuclear resonance vibrational spectroscopy (NRVS)--to study the normal modes of the Fe-S cluster in [(n-Bu)4N]2[Fe4S4(SPh)4]. This [Fe4S4(SR)4]2- complex serves as a model for the clusters in 4Fe ferredoxins and high-potential iron proteins (HiPIPs). The IR spectra exhibited differences above and below the 243 K phase transition.

Borohydride, azide, and chloride anions as terminal ligands on Fe/Mo/S clusters. Synthesis, structure and characterization of [(Cl4-cat)(PPr3) MoFe3S4(X)2]2(Bu4N)4 and [(Cl4-cat)(PPr3)MoFe3S4 (PPr3)(X)]2(Bu4N)2 (X = N3-, BH4-, Cl-) double-fused cubanes. NMR reactivity studies of [(Cl4-cat)(PPr3) MoFe3S4(BH4)2]2(Bu4N)4.

Our explorations of the reactivity of Fe/Mo/S clusters of some relevance to the FeMoco nitrogenase have led to new double-fused cubane clusters with the Mo2Fe6S8 core as derivatives of the known (Cl4-cat)2Mo2Fe6S8(PPr3)6 (I) fused double cubane. The new clusters have been obtained by substitution reactions of the PPr3 ligands with Cl-, BH4-, and N3-. By careful control of the conditions of these reactions, the clusters [(Cl4-cat)(PPr3)MoFe3S4(BH4)2]2(Bu4N)4 (II), [(Cl4-cat)(PPr3)MoFe3S4(PPr3)(BH4)]2(Bu4N)2 (III), [(Cl4-cat)(PPr3)MoFe3S4(N3)2]2(Bu4N)4 (IV), [(Cl4-cat)(PPr3)MoFe3S4(PPr3)(N3)]2(Bu4N)2 (V), and [(Cl4-cat)(PPr3)MoFe3S4Cl2]2(Et4N)4 (VI) have been obtained and structurally characterized.