منابع مشابه
Nucleophilicity of zinc-bound thiolates
The nucleophilicity of biomimetic zinc-thiolate complexes against methyl iodide has been studied. The activation barrier has been computed with the B3LYP functional. The reactivity depends on the global charge, the nature of the ligand set and the presence of hydrogen bonds. This shows that the understanding of zinc site nucleophilicity can not be achieved by the knowledge of the atom donor set...
متن کاملReactivity of polynuclear zinc-thiolate sites
The proton affinities of a series of monoand polynuclear zinc-thiolate compounds, mimicking zing finger protein and metallothioneins sites, have been investigated by Density Functional Theory calculations. This allows to evaluate the intrinsic nucleophilicity of synthetic and natural zinc-bound thiolates and to compare their relative reactivities. The site specificity of the experimental thiola...
متن کاملEnhanced nucleophilicity and depressed electrophilicity of peroxide by zinc(II), aluminum(III) and lanthanum(III) ions.
The binuclear zinc(II) complex, [Zn2(HPTP)(CH3COO)]2+ was found highly active to cleave DNA (double-strand super-coiled DNA, pBR322 and phix174) in the presence of hydrogen peroxide. However, no TBARS (2-thiobarbituric acid reactive substance) formation was detected in a solution containing 2-deoxyribose (or 2'-deoxyguanosine, etc); where (HPTP) represents N,N,N'-N'-tetrakis(2-pyridylmethyl)-1,...
متن کاملDefinition of a nucleophilicity scale.
This work deals with exploring some empirical scales of nucleophilicity. We have started evaluating the experimental indices of nucleophilicity proposed by Legon and Millen on the basis of the measure of the force constants derived from vibrational frequencies using a probe dipole H-X (X = F,CN). The correlation among some theoretical parameters with this experimental scale has been evaluated. ...
متن کاملSynthetic modeling of zinc thiolates: quantitative assessment of hydrogen bonding in modulating sulfur alkylation rates.
A series of mononuclear zinc thiolate complexes have been prepared and fully characterized. The reactions of the complexes with alkyl halides, leading to zinc halides and the corresponding thioethers, have been examined by kinetic methods. In toluene, the reactions obey a second-order rate law displaying activation parameters consistent with a S(N)2 attack of the zinc-bound thiolate on the carb...
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ژورنال
عنوان ژورنال: Comptes Rendus Chimie
سال: 2009
ISSN: 1631-0748
DOI: 10.1016/j.crci.2009.01.002