Oxidation-state and metal-ion dependent stereoisomerization in oxo molybdenum and tungsten complexes of a bulky alkoxy heteroscorpionate ligand

Monooxo Mo(V) complexes of a N2O heteroscorpionate ligand designated (L10O) are found to exist as isolable cis and trans isomers. We have been able to trap the kinetically labile cis isomer and follow its isomerization to the thermodynamically more stable trans form. We have also followed the kinetics of isomerization between the cis and trans isomers of the corresponding dioxo Mo(VI) and W(VI) species. Here the trans is the labile isomer that spontaneously converts to the thermodynamically more stable cis. It is observed that at 60 degrees C in DMSO the Mo(VI) complex isomerizes approximately 6.5 times faster than the Mo(V) and nearly 5 times faster than the corresponding W(VI) analogs. The temperature dependence to the kinetics of the Mo(V) and Mo(VI) isomerizations give activation parameters that are similar for both oxidation states and consistent with those previously observed in [(L1O)MoOCl2] suggesting a similar twist mechanism is operating in all cases. Thus there are oxidation state, metal ion and donor atom dependent differences in isomeric stability that could have significant implications for understanding the mechanisms of both enzymatic and nonenzymatic oxo atom transfer reactions catalyzed by complexes of Mo, W and Re.     

Methylation of (2-methylethanethiol-bis-3,5-dimethylpyrazolyl)methane zinc complexes and coordination of the resulting thioether: relevance to zinc-containing alkyl transfer enzymes

A series of zinc complexes using a new tripodal, N(2)S, heteroscorpionate ligand (L3SH) that is isostructural and isoelectronic with the well-known N(3) trispyrazolylborates have been methylated in solution and the coordination properties of the resulting thioether examined. This system models the reactivity of zinc-containing enzymes involved in alkyl group transfers such as the DNA repair protein Ada from E. coli, or farnasyl transferase where it has been shown that the thioether resulting from alkyl group transfer remains in the coordination sphere of the zinc. The following complexes have been structurally characterized: [(L3S)ZnI] (1), [(L3SCH(3))ZnI(2)] (2), [(L3SCH(3))ZnI]BF(4) (3), [(L3SCH(3))Zn-mu-bis-acetato-mu-hydroxo-Zn(L3SCH(3))]BF(4) (5), [(L3SCH(3))ZnSPh(F5)]ClO(4) (7), and [(L3SCH(3))(2)Zn](BF(4))(2) (8). Complexes 3, 4, 5, 7, and 8 all display thioether coordination. Thus in the absence of superior anionic ligands, thioethers are reasonably good donors to zinc in either a tetrahedral or octahedral geometry. The methylation of the complex [(L3S)ZnSPh(F5)], which contains two different thiols, produces a single product, 7, where only the aliphatic thiol has been alkylated. This observation validates the suggestion that reactivity in enzymes with multiple zinc-bound thiols could be controlled by differences in thiol pK(a) (Hammes, B. S.; Warthen, C. R.; Crans, D.; Carrano, C. J. J. Biol. Inorg. Chem. 2000, 6, 82. Compound 7 is also of interest in that it resembles the metal ion-binding site of the blue copper protein, azurin.     

A fast, convenient and rugged procedure for characterizing the selectivity of alkyl-silica columns

Previous work has shown that the selectivity of reversed-phase columns for HPLC can be described by means of five column parameters: H (hydrophobicity), S* (steric resistance), A (hydrogen-bond acidity), B (hydrogen-bond basicity) and C (cation-exchange capacity). Values of H, S*, etc. can be determined by carrying out retention measurements for 18 test solutes under standardized conditions. The reproducibility of the latter procedure has been evaluated by comparison testing in four different laboratories and found acceptable. An alternative 10-solute test procedure which is more reproducible and convenient (but somewhat less accurate), requires only 2-3 h per column.     

Oxo-molybdenum(VI,V,IV) complexes of the facially coordinating tris(mercaptoimidazolyl)borate ligand: synthesis, characterization, and oxygen atom transfer reactivity

A series of monooxo-Mo(IV,V) and dioxo-Mo(VI) complexes of the "soft" tripodal ligand, sodium tris(mercaptoimidazolyl)borate (NaTm(Me)), have been synthesized as potential oxygen atom transfer (OAT) models for sulfite oxidase. Complexes have been characterized by X-ray crystallography, cyclic voltammetry, and EPR, where appropriate. Oxygen atom transfer kinetics of Tm(Me)MoO(2)Cl, both stoichiometric and catalytic, have been studied by a combination of UV-vis and (31)P NMR spectroscopies under a variety of conditions. OAT rates are consistent with previously established relationships between redox potential/reactivity and mechanistic studies. The analysis of these complexes as potential structural and functional analogues of relevance to molybdoenzymes is further discussed.     

Interaction of oxo-bridged vanadium(III) phenanthroline and bipyridine dimers with DNA

Cationic mu-oxo V(III) dimers of the type [V2OL4Cl2]2+ (L = 1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline; or 2,2'-bipyridine) are shown to interact very strongly with DNA and to lead ultimately to its degradation. Spectroscopic binding studies, electrophoreses, DNA melting temperature experiments, and other tests on the parent 1,10-phenthroline complex all yield results consistent with tight binding. However, the exact nature of the binding--i.e., intercalative, groove binding, electrostatic, or covalent--remains unclear. Resonance Raman spectroscopy is found to be a powerful method for studying the interaction of these mu-oxo V(III) dimers with DNA and shows that in frozen aqueous solution, the parent complex [V2O(phen)4Cl2]2+ undergoes initial aquation, followed by the reaction of the aquated species with the DNA. Once the V(III) dimer is bound to the DNA, redox takes place, leading to the formation of alkaline-sensitive lesions. Hydrogen peroxide is implicated as a partner in this redox event, based on the effects of the enzymes SOD and catalase.     

Cobalt, zinc, and nickel complexes of a diatopic heteroscorpionate ligand: building blocks for coordination polymers

New binuclear complexes of Co(II), Zn(II), and Ni(II) derived from a diatopic heteroscorpionate ligand, (4-carboxyphenyl)bis(3,5-dimethylpyrazolyl)methane (L4c), have been synthesized and characterized by X-ray diffraction, ESI-MS, IR, UV-vis spectroscopy, and magnetic susceptibility. These building blocks have been subsequently used for the construction of higher order metallosupramolecular architectures.