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Reactivity of polynuclear zinc‐thiolate sites
Author(s) -
Ohanessian Gilles,
Picot Delphine,
Frison Gilles
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22866
Subject(s) - chemistry , zinc , reactivity (psychology) , nucleophile , affinities , density functional theory , alkylation , zinc finger , lewis acids and bases , cluster (spacecraft) , stereochemistry , electrophile , computational chemistry , crystallography , organic chemistry , catalysis , biochemistry , medicine , alternative medicine , pathology , computer science , transcription factor , gene , programming language
The proton affinities of a series of mono‐ and polynuclear zinc‐thiolate compounds, mimicking zing finger protein and metallothioneins (MTs) 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 thiolate alkylation for the Zn 4 Cys 11 clusters in MTs is well reproduced, as well as the relative reactivities of ZnHis 2 Cys 2 , ZnHisCys 3 , and ZnCys 4 zinc finger sites. Our results also show that terminal thiolates, bound to only one Lewis acid, are more reactive than bridging thiolates. Synthetic inorganic clusters and the Zn 4 Cys 9 His 2 cluster found in a cyanobacterial MT are less reactive than Zn 4 Cys 11 and Zn 3 Cys 9 clusters in MTs. These results allow discussing the influence of the protein backbone and residues on the reactivity of these natural clusters. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011