Crystal structures of Zn(SR)2 complexes: structural models for the proposed [Zn(cys-S)2(his)2] center in transcription factor IIIA and related nucleic acid binding proteins

Corwin, Douglas T.; Koch, Stephen A.

doi:10.1021/ic00276a011

Cited by 86 publications

(30 citation statements)

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“…Bonds formed by ammine ligands are closer to the lower limit, being comparable e. g. to those of 2.024±2.054 A Ê found in the Zn(NH 3 ) 4 2+ cation [18]. Bonds to 2-picoline or 2,4-lutidine in 3 and 4 have almost the same length as those previously reported for other Zn complexes containing heterocyclic nitrogen ligands [6,19,20].…”

Section: Description Of Structuressupporting

confidence: 83%

Zinc(II) Tri-tert-butoxysilanethiolates. Synthesis, Properties, Crystal and Molecular Structures of [Zn{SSi(OBut)3}2(NH3)L] (L = 2-Picoline or 2,4-Lutidine) and [Zn{SSi(OBut)3}2(NH3)2] · MeCN Complexes

Becker

Dołęga

Konitz

et al. 2001

Z. anorg. allg. Chem.

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Zn{SSi(OBu t ) 3 } 2 (NH 3 )] 2 (1) reacts with 2-picoline or 2,4-lutidine (L) without elimination of ammonia giving stable monometallic complexes [Zn{SSi(OBu t ) 3 } 2 (NH 3 )L] (3 and 4), with two different nitrogen ligands bonded to the metal center. Reaction of (Bu t O) 3 SiSH with zinc di(acetylacetonate) in ammonia atmosphere leads to the complex with two ammine ligands [Zn{SSi(OBu t ) 3 } 2 (NH 3 ) 2 ]´MeCN (5). Molecular and crystal structures of 3, 4 and 5 have been determined by the single crystal X-ray structural analysis. All have distorted tetrahedral geometry. The presence of ammonia gives rise to hydrogen bonds, different in all three cases. 3, 4, and 5 are the first examples of structurally characterized ammine ligated zinc thiolates.Beitra È ge zur Chemie der Silicium±Schwefel Verbindungen. 76. Zink(II) Tri-tert-butoxysilanthiolate. Darstellung, Eigenschaften, Kristallund Moleku È lstrukturen von [Zn{SSi(OBu t ) 3 } 2 (NH 3 )L] (L = 2-Picolin oder 2,4-Lutidin) und [Zn{SSi(OBu t ) 3 } 2 (NH 3 ) 2 ]´MeCN Inhaltsu È bersicht. [Zn{SSi(OBu t ) 3 } 2 (NH 3 )] 2 (1) reagiert mit 2-Picolin oder 2,4-Lutidin (L) ohne Eliminierung von Ammoniak unter Bildung von stabilen monometallischen Komplexen [Zn{SSi(OBu t ) 3 } 2 (NH 3 )L] (3 und 4), mit zwei verschiedenen stickstoffhaltigen Liganden am Metall-Zentrum. Eine Umsetzung von (Bu t O) 3 SiSH mit Zink-Acetylacetonat in einer Atmospha È re von Ammoniak ergab einen Komplex mit zwei Ammoniak-Liganden [Zn{SSi(OBu t ) 3 } 2 (NH 3 ) 2 ]´M eCN (5). Die Moleku È l-und Kristallstrukturen von 3, 4 und 5 wurden ro È ntgenographisch bestimmt. Alle Verbindungen zeigen eine Abweichung von einer tetraedrischen Geometrie. Die Anwesenheit von Ammoniak fu È hrt zu Wasserstoffbru È ckenbindungen die sich in alle drei Fa È llen unterscheiden. Verbindungen 3, 4 und 5 sind die ersten, strukturell charakterisierten Zink-Thiolate in welchen Zink noch an Ammoniak gebunden ist.

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Section: Description Of Structuressupporting

confidence: 83%

Zinc(II) Tri-tert-butoxysilanethiolates. Synthesis, Properties, Crystal and Molecular Structures of [Zn{SSi(OBut)3}2(NH3)L] (L = 2-Picoline or 2,4-Lutidine) and [Zn{SSi(OBut)3}2(NH3)2] · MeCN Complexes

Becker

Dołęga

Konitz

et al. 2001

Z. anorg. allg. Chem.

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“…It has been shown that the M -S dis tances in analogous complexes of a given metal [24,28], Conse quently, the C d -S distance in [Cd(pymt)2phen] is unusually short.…”

Section: R Esults and Discussionmentioning

confidence: 99%

Direct Electrochemical Synthesis of Pyrimidine-2-thionato Complexes of Zinc(II) and Cadmium(II): The Crystal Structure of (1,10-Phenanthroline)bis(pyrimidine-2-thionato)cadmium(II)

Castro

Durán

García‐Vázquez

et al. 1992

Zeitschrift Für Naturforschung B

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Zn(pymt)2 and Cd(pymt)2 complexes have been obtained by electrochemical oxidation o f anodic zinc or cadmium in acetonitrile solutions o f pyrimidine-2-thione (Hpymt). W hen 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) was added to the electrochemical cell, the adducts [M (pymt)2(bipy)], or [M(pymt)2(phen)] (M = Zn or Cd) were obtained. Crystals o f [Cd(pymt)2phen] are orthorhombic, with a = 9.882(2), b = 12.491(1), c = 16.513(2)A, space group P 2,2,2, and Z = 4. The cadmium atom has distorted octahedral geometry, and one ni trogen atom o f each pyrimidine-2-thiolato ligand is not coordinated.

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“…Furthermore, the sulfur atoms of the thiol groups of cysteine and methionine are potential ligands. Distances between zinc and (N/O) (meaning nitrogen or oxygen) of 2.03-2.12 Å and between zinc and sulfur of 2.25-2.36 Å have been observed in proteins [14,15,23,30,31] and in synthetic zinc compounds [32,33].…”

Section: R E S U L T Smentioning

confidence: 99%

The role of zinc in the methylation of the coenzyme M thiol group in methanol:coenzyme M methyltransferase from Methanosarcina barkeri

Krüer

Haumann

Meyer‐Klaucke³

et al. 2002

European Journal of Biochemistry

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Methanol:coenzyme M methyltransferase from methanogenic archaea is a cobalamin-dependent enzyme composed of three different subunits: MtaA, MtaB and MtaC. MtaA is a zinc protein that catalyzes the methylation of coenzyme M (HS-CoM) with methylcob(III)alamin. We report zinc XAFS (X-ray absorption fine structure) results indicating that, in the absence of coenzyme M, zinc is probably coordinated by a single sulfur ligand and three oxygen or nitrogen ligands. In the presence of coenzyme M, one (N/O)-ligand was replaced by sulfur, most likely due to ligation of the thiol group of coenzyme M. Mutations in His237 or Cys239, which are proposed to be involved in ligating zinc, resulted in an over 90% loss in enzyme activity and in distinct changes in the zinc ligands. In the His237 fi Ala and Cys239 fi Ala mutants, coenzyme M also seemed to bind efficiently by ligation to zinc indicating that some aspects of the zinc ligand environment are surprisingly uncritical for coenzyme M binding. Keywords:1 1 zinc enzymes; methanogenic archaea; methyl transferases; thiol group alkylation; EXAFS.Methanosarcina barkeri and other Methanosarcina species can grow on methanol as carbon source which is disproportionated to CH 4 and CO 2 [1]. The first step in this metabolic pathway is the formation of methyl-coenzyme M (CH 3 -S-CoM) from methanol and coenzyme M (HS-CoM) [2].The reaction is catalyzed by methanol:coenzyme M methyltransferase which is composed of the three subunits MtaA (35.9 kDa), MtaB (50.7 kDa) and MtaC (27.9 kDa), of which MtaC is a corrinoid protein. They catalyze the following partial reactions [3][4][5][6][7].MtaA is a zinc protein [3,7,8] that also catalyzes the methylation of coenzyme M with methylcob(III)alamin [9]. Several isoenzymes of MtaA, designated MtbA and MtsA have been found [9][10][11].The methylation of coenzyme M to methyl-coenzyme M is a reaction in which a thiol group is alkylated. Enzymes catalyzing alkyl transfers to thiols have all been found to be zinc proteins [12] [19]. The postulated role of zinc in these enzymes is that of a Lewis acid that activates the thiol group to be alkylated. Coordination of the thiol group to the active site zinc has been shown by extended X-ray absorption fine structure (EXAFS) spectroscopy [14,15], by UV spectroscopy [20] and in the case of protein farnesyl transferase by crystal structure analysis [19]. It results in a decrease in the pK value of the thiol group as shown by the release of a proton upon binding of the substrate to the zinc enzyme [21].MtaA does not share sequence similarity to any of the other zinc enzymes catalyzing thiol group alkylation [8,22]. Abbreviations: HS-CoM, coenzyme M; CH 3 -S-CoM, methyl-coenzyme M; EXAFS, extended X-ray absorption fine structure; Mta, methanol:coenzyme M methyltransferase; MtaA, protein subunit of Mta; XANES, X-ray absorption near edge structure; XAS, X-ray absorption spectroscopy.

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Crystal structures of Zn(SR)2 complexes: structural models for the proposed [Zn(cys-S)2(his)2] center in transcription factor IIIA and related nucleic acid binding proteins

Cited by 86 publications

References 1 publication

Zinc(II) Tri-tert-butoxysilanethiolates. Synthesis, Properties, Crystal and Molecular Structures of [Zn{SSi(OBut)3}2(NH3)L] (L = 2-Picoline or 2,4-Lutidine) and [Zn{SSi(OBut)3}2(NH3)2] · MeCN Complexes

Zinc(II) Tri-tert-butoxysilanethiolates. Synthesis, Properties, Crystal and Molecular Structures of [Zn{SSi(OBut)3}2(NH3)L] (L = 2-Picoline or 2,4-Lutidine) and [Zn{SSi(OBut)3}2(NH3)2] · MeCN Complexes

Direct Electrochemical Synthesis of Pyrimidine-2-thionato Complexes of Zinc(II) and Cadmium(II): The Crystal Structure of (1,10-Phenanthroline)bis(pyrimidine-2-thionato)cadmium(II)

The role of zinc in the methylation of the coenzyme M thiol group in methanol:coenzyme M methyltransferase from Methanosarcina barkeri

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