ABSTRACT
A series of hydrochalcogenido and phenylchalcogenolate complexes of zinc supported by tris(2-mercapto-1-tert-butylimidazolyl)hydroborato ligation, [Tm(Bu(t))]ZnEH (E = S, Se) and [Tm(Bu(t))]ZnEPh (E = O, S, Se, Te) have been synthesized from [Tm(Bu(t))]ZnMe; structural characterization by X-ray diffraction indicates that the variation in Zn-E bonding as a function of the chalcogen is significantly different from that in other series of metal-chalcogenolate compounds.
ABSTRACT
The molecular structure of the tris(2-mercapto-1-tolylimidazolyl)hydroborato complex [[Tm(p-Tol)]Zn(mim(p-Tol))][ClO(4)].3MeCN has been determined by X-ray diffraction, thereby demonstrating that the mim(p-Tol) ligand exhibits a N-H...O hydrogen bond with the [ClO(4)](-) counterion, [[Tm(p-Tol)]Zn(mim(p-Tol))...(OClO(3))], rather than hydrogen bond with a sulfur of the [Tm(p-Tol)] ligand. DFT calculations on a series of related complexes, namely [[Tm(Me)]Zn(mim(Me))](+), [[Tm(Me)]Zn(mim(Me))]...(OClO(3))], [[Tm(Me)]Zn(mim(Me))]...[O(H)Me]](+), and [[Tm(Me)]Zn(mim(Me))]...(NCMe)](+) demonstrate that an intramolecular N-H...S hydrogen bond within [[Tm(Me)]Zn(mim(Me))](+) is also less favored than the corresponding hydrogen bonding interactions with MeCN, MeOH, and [ClO(4)](-). The inability of the sulfur atoms of [Tm(R)] ligand to act as an effective hydrogen bond acceptor is in marked contrast to the ability of sulfur atoms in thiolate ligands to participate in the formation of N-H...S hydrogen bonds, an observation that reflects the "thione"versus"thiolate" nature of the [Tm(R)] ligand.
Subject(s)
Imidazoles/chemistry , Organometallic Compounds/chemistry , Crystallography, X-Ray , Hydrogen Bonding , Ligands , Models, Molecular , Molecular StructureABSTRACT
The dimethylsulfoxide reductase (DMSOR) from Rhodobacter capsulatus is known to retain its three-dimensional structure and enzymatic activity upon substitution of molybdenum, the metal that occurs naturally at the active site, by tungsten. The redox properties of tungsten-substituted DMSOR (W-DMSOR) have been investigated by a dye-mediated reductive titration with the concentration of the W(V) state monitored by EPR spectroscopy. At pH 7.0, E(m)(W(VI)/W(V)) is -194 mV and E(m)(W(V)/W(IV)) is -134 mV. Each E(m) value of W-DMSOR is significantly lower (220 and 334 mV, respectively) than that of the corresponding couple of Mo-DMSOR. These redox potentials are consistent with the ability of Mo-DMSOR to catalyze both the reduction of DMSO to DMS and the back reaction, whereas W-DMSOR is very effective in catalyzing the forward reaction, but shows no ability to catalyze the oxidation of DMS to DMSO.
Subject(s)
Iron-Sulfur Proteins , Oxidoreductases/chemistry , Rhodobacter capsulatus/enzymology , Tungsten/chemistry , Catalysis , Dimethyl Sulfoxide/chemistry , Dimethyl Sulfoxide/metabolism , Electron Spin Resonance Spectroscopy , Hydrogen-Ion Concentration , Molybdenum/chemistry , Molybdenum/metabolism , Oxidation-Reduction , Oxidoreductases/metabolism , Titrimetry/methods , Tungsten/metabolismABSTRACT
The electronic influence of unbridged and ansa-bridged ring substituents on a zirconocene center has been studied by means of IR spectroscopic, electrochemical, and computational methods. With respect to IR spectroscopy, the average of the symmetric and asymmetric stretches (nu(CO(av))) of a large series of dicarbonyl complexes (Cp(R))(2)Zr(CO)(2) has been used as a probe of the electronic influence of a cyclopentadienyl ring substituent. For unbridged substituents (Me, Et, Pr(i), Bu(t), SiMe(3)), nu(CO(av)) on a per substituent basis correlates well with Hammett sigma(meta) parameters, thereby indicating that the influence of these substituents is via a simple inductive effect. In contrast, the reduction potentials (E degrees ) of the corresponding dichloride complexes (Cp(R))(2)ZrCl(2) do not correlate well with Hammett sigma(meta) parameters, thereby suggesting that factors other than the substituent inductive effect also influence E degrees. Ansa bridges with single-atom linkers, for example [Me(2)C] and [Me(2)Si], exert a net electron-withdrawing effect, but the effect is diminished upon increasing the length of the bridge. Indeed, with a linker comprising a three-carbon chain, the [CH(2)CH(2)CH(2)] ansa bridge becomes electron-donating. In contrast to the electron-withdrawing effect observed for a single [Me(2)Si] ansa bridge, a pair of vicinal [Me(2)Si] ansa bridges exerts an electron-donating effect relative to that from the single bridge. DFT calculations demonstrate that the electron-withdrawing effect of the [Me(2)C] and [Me(2)Si] ansa-bridges is due to stabilization of the cyclopentadienyl ligand acceptor orbital, which subsequently enhances back-donation from the metal. The calculations also indicate that the electron-donating effect of two vicinal [Me(2)Si] ansa bridges, relative to that of a single bridge, is a result of it enforcing a ligand conformation that reduces back-donation from the metal.
