Metal-thiolate bonds in bioinorganic chemistry.

Metal-thiolate bonds in bioinorganic chemistry. Research Abstract Details 

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Metal-thiolate bonds in bioinorganic chemistry. Abstract Text:

Edward I Solomon,Serge I Gorelsky,Abhishek Dey,

Metal-thiolate active sites play major roles in bioinorganic chemistry. The M--S(thiolate) bonds can be very covalent, and involve different orbital interactions. Spectroscopic features of these active sites (intense, low-energy charge transfer transitions) reflect the high covalency of the M--S(thiolate) bonds. The energy of the metal-thiolate bond is fairly insensitive to its ionic/covalent and pi/sigma nature as increasing M--S covalency reduces the charge distribution, hence the ionic term, and these contributions can compensate. Thus, trends observed in stability constants (i.e., the Irving-Williams series) mostly reflect the dominantly ionic contribution to bonding of the innocent ligand being replaced by the thiolate. Due to high effective nuclear charges of the Cu(II) and Fe(III) ions, the cupric- and ferric-thiolate bonds are very covalent, with the former having strong pi and the latter having more sigma character. For the blue copper site, the high pi covalency couples the metal ion into the protein for rapid directional long range electron transfer. For rubredoxins, because the redox active molecular orbital is pi in nature, electron transfer tends to be more localized in the vicinity of the active site. Although the energy of hydrogen bonding of the protein environment to the thiolate ligands tends to be fairly small, H-bonding can significantly affect the covalency of the metal-thiolate bond and contribute to redox tuning by the protein environment.

Metal-thiolate bonds in bioinorganic chemistry. Publishing Authors By Initials

EI Solomon,SI Gorelsky,A Dey,

For similar sulfhydryl compounds research abstracts see: sulfhydryl compounds research

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Metal-thiolate bonds in bioinorganic chemistry. Journal Published:

PUBLICATION TYPE: Review

Journal: Journal of computational chemistry

VOLUME: 27

Page Numbers: 1415-28

Journal Abbreviation:

ISSN: 0192-8651

DAY: 3

MONTH: Sep

YEAR: 2006

Metal-thiolate bonds in bioinorganic chemistry. Information

Number of References: 46

LANGUAGE: eng

NlmUniqueID: 9878362

Metal-thiolate bonds in bioinorganic chemistry. Keywords Mesh Terms:

KEYWORDS: Sulfhydryl Compounds

MESH TERMS: chemistry

Chemical & Substance for Abstract: Metal-thiolate bonds in bioinorganic chemistry. Information

Substance Name: Sulfhydryl Compounds

Registry Number: 0

Grant and Affiliation Information for Metal-thiolate bonds in bioinorganic chemistry.

AFFILIATION: Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, California 94305, USA. Edward.Solomon@stanford.edu

Country: United States

AGENCY: United States NIGMS

GRANT: GM-2FBM405

ACRONYM: GM

MEDLINETA: J Comput Chem

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