Structural chemistry of complexes of ( ? 1)d s metal ions with ?-N-donor substituted thiolate ligands (=0, 2)

Fleischer, Holger

doi:10.1016/j.ccr.2004.08.024

Cited by 59 publications

(20 citation statements)

References 101 publications

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“…International Journal of Inorganic Chemistry 4 ] with atom labels and 50% probability displacement ellipsoids for non-H atoms.…”

Section: Resultsmentioning

confidence: 99%

“…Among these materials, chlorocadmate compounds have been of special interest for their structural flexibility. Complexes with Cd(II) centers have been at the center of growing interest due to their variable frameworks, and their potential photoluminescent and nonlinear optical (NLO) properties [3,4]. They can occur as simple tetrahedral anions CdX 2− 4 or form the backbone of chain polymers.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Bis(4-methylbenzylammonium) Tetrachloridocadmate(II)

Kefi¹,

Zeller

Lefèbvre

et al. 2011

International Journal of Inorganic Chemistry

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The crystal structure of the new inorganic-organic hybrid compound [4-CH 3 C 6 H 4 CH 2 NH 3 ] 2 [CdCl 4 ] has been determined by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Pnma with lattice parameters a = 10.721(2), b = 33.986(6), c = 5.326(1)Å, β = 97.222(1)• , V = 1940.8(7)Å 3 , and Z = 4. The framework of the title compound is built upon layers parallel to (010) made up from corner-sharing CdCl 6 octahedra. 4-Methylbenzylammonium cations are situated between the layers and connect them via an N-H· · · Cl hydrogen bonding network. The Cd atom is located on an inversion centre, and the coordination environment is described as distorted octahedral. Solid state 13 C CP-MAS NMR spectroscopy is in agreement with the X-ray structure. DFT calculations allow the attribution of the carbon peaks to the independent crystallographic sites. Thermal analysis and infrared spectroscopy were also used to characterize the complex.

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“…International Journal of Inorganic Chemistry 4 ] with atom labels and 50% probability displacement ellipsoids for non-H atoms.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Bis(4-methylbenzylammonium) Tetrachloridocadmate(II)

Kefi¹,

Zeller

Lefèbvre

et al. 2011

International Journal of Inorganic Chemistry

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“…They are of special interest in bioinorganic chemistry because of the search for simple model compounds for metal-proteins [1][2][3][4][5]. These ligands exist in the N=CSH and NC=S forms exhibiting a thiol-thione equilibrium [6,7].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of dibromo-bis(1,3-imidazolidine-2-thione-S)zinc(II), ZnBr2(C3H6N2S)2

Fettouhi

Wazeer

Isab

2006

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialZinc bromide was dissolved in minimum amount of water. Two molar equivalents of the thione were dissolved in methanol. The mixture of both solutions was refluxed for three hours and filtered. The filtrate was allowed to evaporate slowly and a white crystalline product was obtained (m.p. 175°C). Elemental analysis found: C, 17.10 %; H, 2.68 %; N, 12.74 %; calc. for C 6H12N4ZnBr2S2: C, 16.77 %; H, 2.79 %; N, 13.08 %. Experimental detailsHydrogen atoms were included at calculated positions using a riding model. An sp 2 hybridization was assumed for the nitrogen atoms of the NH groups. DiscussionComplexes of heterocyclic ligands such as imidazolidine-2-thione (imt) and its derivatives with metal ions have been widely investigated in recent years. They are of special interest in bioinorganic chemistry because of the search for simple model compounds for metal-proteins [1][2][3][4][5]. These ligands exist in the N=CSH and NC=S forms exhibiting a thiol-thione equilibrium [6,7]. However, it has been established that the thione form dominates in the solid state [8]. We have studied extensively the interaction of metal ions with imidazolidine-2-thione and its derivatives [9][10][11][12]. In the title compound, the metal ion is bound to two bromide ions and the S atoms of two imidazolidine thione ligand molecules. The four-coordinate complex has a distorted tetrahedral geometry. The bond angles are in the range of 107.28(3)° 111.60(2)°a nd the average ZnS and ZnBr bond lengths are 2.3450(8) Å and 2.3957(5) Å, respectively. The bond distances are in agreement with those reported for the complex dibromo-bis(1-t-butyl-4-imidazolidine-2-thione)zinc [13], the later being much more distorted (100.61 (2)

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“…c Distance between hexacoordinated Mg 2+ and the sulfur atom of thiolates (Englich and Ruhlandt-Senge 2000). Distance between hexacoordinated Cd 2+ and the sulfur atom of thiolates (Fleischer 2005).…”

Section: Determination Of Rate and Equilibrium Constantsmentioning

confidence: 99%

Modulation of individual steps in group I intron catalysis by a peripheral metal ion

Forconi¹,

Piccirilli²,

Herschlag³

2007

RNA

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Enzymes are complex macromolecules that catalyze chemical reactions at their active sites. Important information about catalytic interactions is commonly gathered by perturbation or mutation of active site residues that directly contact substrates. However, active sites are engaged in intricate networks of interactions within the overall structure of the macromolecule, and there is a growing body of evidence about the importance of peripheral interactions in the precise structural organization of the active site. Here, we use functional studies, in conjunction with published structural information, to determine the effect of perturbation of a peripheral metal ion binding site on catalysis in a well-characterized catalytic RNA, the Tetrahymena thermophila group I ribozyme. We perturbed the metal ion binding site by site-specifically introducing a phosphorothioate substitution in the ribozyme's backbone, replacing the native ligands (the pro-R P oxygen atoms at positions 307 and 308) with sulfur atoms. Our data reveal that these perturbations affect several reaction steps, including the chemical step, despite the absence of direct contacts of this metal ion with the atoms involved in the chemical transformation. As structural probing with hydroxyl radicals did not reveal significant change in the three-dimensional structure upon phosphorothioate substitution, the effects are likely transmitted through local, rather subtle conformational rearrangements. Addition of Cd 2+ , a thiophilic metal ion, rescues some reaction steps but has deleterious effects on other steps. These results suggest that native interactions in the active site may have been aligned by the naturally occurring peripheral residues and interactions to optimize the overall catalytic cycle.

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Structural chemistry of complexes of ( ? 1)d s metal ions with ?-N-donor substituted thiolate ligands (=0, 2)

Cited by 59 publications

References 101 publications

Synthesis and Characterization of Bis(4-methylbenzylammonium) Tetrachloridocadmate(II)

Synthesis and Characterization of Bis(4-methylbenzylammonium) Tetrachloridocadmate(II)

Crystal structure of dibromo-bis(1,3-imidazolidine-2-thione-S)zinc(II), ZnBr2(C3H6N2S)2

Modulation of individual steps in group I intron catalysis by a peripheral metal ion

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