[Show abstract][Hide abstract] ABSTRACT: In our effort to study vanadium chalcogenide chemistry, we have synthesized and characterized a class of non-oxido divanadium(iv) and divanadium(v) complexes with chalcogenide and dichalcogenide as bridges. All structures consist of a similar divanadium motif, in which two metal centers are bridged by one μ-chalcogenide and one μ-η(2):η(2)-dichalcogenide, forming a V2(μ-E)(μ-η(2):η(2)-E2) (E = S or Se) core structure. These compounds are [V(IV)2(PS3)2(μ-Se2)(μ-Se)][PPh4]2 (), [V(V)2(PS3'')2(μ-Se2)(μ-Se)] (), [V(V)2(PS3'')2(μ-S2)(μ-S)] () and [V(V)2(PS3)2(μ-S2)(μ-S)] () ([PS3](3-) = P(C6H4-2-S)3 and [PS3''](3-) = P(C6H3-3-SiMe3-2-S)3). Compound exhibits diamagnetic behavior, indicating strong antiferromagnetic coupling between two d(1) centers. Compounds and have the highest oxidation states for vanadium ions (+5/+5) among those reported divanadium chalcogenide clusters. The work demonstrates that high-valent divanadium chalcogenide clusters can be obtained with the activation of elemental chalcogens by low-valent vanadium ions.
[Show abstract][Hide abstract] ABSTRACT: To provide the mechanistic information of nitrogenase at a molecular level, much effort has been made to develop synthetic metal complexes that have enzyme-like reactivity. Herein we obtain an iron(II) complex binding with a tris(thiolato)phosphine ligand, [P(Ph)4][Fe(PS3″)(CH3CN)] [1; PS3″ = P(C6H3-3-Me3Si-2-S)3(3-)] that catalyzes the reduction of hydrazine, an intermediate and a substrate of nitrogenase. The substrate- and product-bound adducts, [N(Bu)4][Fe(PS3″)(N2H4)] (2) and [N(Et)4][Fe(PS3″)(NH3)] (3), respectively, are also synthesized. This work provides the feasibility that the late stage of biological nitrogen fixation can be conducted at a single iron site with a sulfur-rich ligation environment.
[Show abstract][Hide abstract] ABSTRACT: A V(III) thiolate complex activated C-Cl bond in dichloromethane via S-based nucleophilic attack. The reaction products, a V(III)-Cl species (major one) and a V(IV) binding to a CH(2) containing ligand (minor one) were obtained. The work demonstrates sulfur donors in the early-transition metal thiolates having strong nucleophilic characteristics.
Chemical Communications 01/2013; 49(11). DOI:10.1039/c2cc37801a · 6.83 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: In the title compound, [N(C(4)H(9))(4)][V(C(23)H(21)NS(3)Si)(2)]·4CH(3)CN, the V(III) atom (site symmetry ) is coordinated by two N,S,S'-tridentate 4,4'-dimethyl-2,2'-(3,7-dimethyl-1H-4,2,1-benzothiaza-siline-1,1-di-yl)dibenzene-thiol-ate ligands in a distorted trans-VN(2)S(4) octa-hedral geometry. The complete cation is generated by crystallographic twofold symmetry, with the V atom lying on the rotation axis. The unusual ligand arose from nucleophilic attack on the coordinated nitrile by the thiol-ate precursor and reduction of nitrile to the imidate.
[Show abstract][Hide abstract] ABSTRACT: Two dinuclear oxovanadium(IV) thiolate complexes, [N(C5H11)4]2[VOL1]2 (1) and [N(C4H9)4][(VOL2)2(mu-OCH3)] (2) (where L1 = [(CH3)SiO(C6H4-2-S)2]3- and L2 = [(C6H5)PO(C6H4-2-S)2]2-), have been synthesized and characterized. The geometry of the anion in 1 can be classified to an edge-sharing bi-square-pyramid with a syn-orthogonal configuration. The one in 2 can be view as a face-sharing bioctahedron with two oxo groups in syn positions. Of note, these two complexes display intramolecular ferromagnetic interaction between two metal centers.