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Journal articles on the topic 'Metal thiolates'

Author: Grafiati

Published: 6 September 2023

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1

TYAPOCHKIN, EDUARD M., and EVGUENII I. KOZLIAK. "Interactions of cobalt tetrasulfophthalocyanine with thiolate anions in dimethylformamide." Journal of Porphyrins and Phthalocyanines 05, no. 04 (April 2001): 405–14. http://dx.doi.org/10.1002/jpp.341.

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Thiolate complexes of cobalt tetrasulfophthalocyanine ( CoTSPc ), possible intermediates of the industrial removal of mercaptans from oil fractions (Merox process), were studied in dimethylformamide, dimethylsulfoxide, and other polar aprotic solvents by UV-vis, 1 H NMR, and ESR spectroscopy. All thiolates react with Co II TSPc under anaerobic conditions with 1:1 stoichiometry. All tested aliphatic thiolates, regardless of their basicity, reduce Co II TSPc to form Co I TSPc derivatives. Low-basicity thiolates also form unstable non-reduced ( RS -) Co II TSPc complexes as dead-end products. Indirect kinetic evidence was obtained for electron transfer from the axial ligand to metal via the phthalocyanine equatorial ligand. 1 H NMR and binding studies revealed sulfur–cobalt interactions in the Co I TSPc product, thus indicating an axial ligand attachment to Co I TSPc . Low-basicity aromatic thiolates (pentachloro- and pentafluorobenzenethiolate) form ( RS -) Co II TSPc complexes, which are stable toward intramolecular metal reduction. This effect is indicative of possible π-stacking between the aromatic thiolate and phthalocyanine ring.

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2

NAVID, ALI, EDUARD M. TYAPOCHKIN, CHARLES J. ARCHER, and EVGUENII I. KOZLIAK. "UV-vis and Binding Studies of Cobalt Tetrasulfophthalocyanine–Thiolate Complexes as Intermediates of the Merox Process." Journal of Porphyrins and Phthalocyanines 03, no. 07 (October 1999): 654–66. http://dx.doi.org/10.1002/(sici)1099-1409(199908/10)3:6/7<654::aid-jpp189>3.0.co;2-l.

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Intermediates of the cobalt tetrasulfophthalocyanine ( CoTSPc )-catalyzed thiol autoxidation were studied by UV-vis spectroscopy. All thiolates react with CoTSPc resulting in the formation of 1:1 complexes. Three major factors control both the stability and aggregation of the complexes: thiolate basicity, metal-to-ligand charge transfer (MLCT) and π stacking. Basic thiolates partially reduce C oII TSPc , whereas CoTSPc complexes with low-basicity aliphatic thiolates ( p K a < 4) do not exhibit Co (II) reduction, based on the absence of the characteristic Co (I) charge transfer band at 450 nm. CoTSPc complexes with aliphatic and bulky aromatic thiolates appear to be aggregated in aqueous solutions and are characterized by a broad band at 650 nm. Non-bulky aromatic thiolates of low basicity ( p K a < 6) form unique stable monomeric Co II TSPc complexes. This unique spectral feature can be attributed to π stacking between the phthalocyanine ring and thiolate. Comparison of binding constants shows that the partial reduction of Co (II) significantly contributes to the thiolate binding. A combination of aromatic π stacking and MLCT appears to be responsible for the observed 1000-fold stronger binding of non-basic aromatic thiolates as compared with aliphatic ligands of similar basicity. Kinetic studies confirm the importance of the thiolate binding type for catalysis.

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3

Wark, Teresa A., and Douglas W. Stephan. "Rhodium induced titanium–sulfur bond cleavage: crystal and molecular structure of ((COD)Rh(μ-SMe))2." Canadian Journal of Chemistry 68, no. 4 (April 1, 1990): 565–69. http://dx.doi.org/10.1139/v90-086.

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Reactions of Ti(III) and Ti(IV) thiolates with Rh complexes have been investigated. In the reaction of Cp2Ti(SMe)2 and [(COD)2Rh]BF4 or [(COD)Rh(sol)2]PF6, thiolate abstraction yields ((COD)Rh(μ-SMe))2, 1. Reaction of (Cp2Ti(μ-SMe))2 with ((COD)Rh(μ-Cl))2 results in ligand exchange affording (Cp2Ti(μ-Cl))2 and 1. The complex 1 crystallizes in the monoclinic space group P21/n, with a = 8.551(2) Å, b = 10.058(3) Å, c = 22.187(4) Å, β = 92.54(1)°, Z = 4, and V = 1906(1) Å3. The structural data show a relatively short approach between the Rh centres (2.948 Å) and between the bridging sulfur atoms (2.888 Å). The implications of these structural features in terms of metal–metal and sulphur–sulfur bonding are discussed. In addition, the implications of these results with respect to the formation of thiolato-bridged, early–late heterobimetallics is considered. Keywords: thiolate abstraction, rhodium thiolate bridged dimer.

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4

Weigand, Wolfgang. "Metallkomplexe mit funktionalisierten Schwefelliganden, I / Metal Complexes of Functionalized Sulphur Containing Ligands, I." Zeitschrift für Naturforschung B 46, no. 10 (October 1, 1991): 1333–37. http://dx.doi.org/10.1515/znb-1991-1010.

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Complexes of the types cis-L2PtCl2 (L = PPh3, 1/2 dppe) and cpRu(PPh3)2Cl react with 1-alkyne-1-thiolates to give the products trans-(Ph3P)2Pt(S–C≡C–Ph)2 (5), dppePt(S–C≡C–Ph)2 (6) and CpRu(PPh3)2(S–C≡C–Ph) (7), respectively. CpRu(PPh3)(CO)(S–C≡C–Ph) (8) is formed by reaction of 7 in an atmosphere of CO. The 2-propene-1-thiolato complexes dppePt(S–CH2–CH = CH2)2 (9), CpFe(CO)2(S–CH2–CH=CH2) (12) and CpFe(PPh3)(CO)(S–CH2–CH=CH2) (13) are obtained from dppePtCl2, CpFe(CO)2I, CpFe(PPh3)(CO)I and lithium or sodium 2-propene-1-thiolate. The complexes are characterized by IR and 1H,13C and 31P NMR spectroscopy.

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5

Stephan, Douglas W., and T. Timothy Nadasdi. "Early transition metal thiolates." Coordination Chemistry Reviews 147 (January 1996): 147–208. http://dx.doi.org/10.1016/0010-8545(95)01134-x.

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6

Ungor, Dékány, and Csapó. "Reduction of Tetrachloroaurate(III) Ions With Bioligands: Role of the Thiol and Amine Functional Groups on the Structure and Optical Features of Gold Nanohybrid Systems." Nanomaterials 9, no. 9 (August 29, 2019): 1229. http://dx.doi.org/10.3390/nano9091229.

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In this review, the presentation of the synthetic routes of plasmonic gold nanoparticles (Au NPs), fluorescent gold nanoclusters (Au NCs), as well as self-assembled Au-containing thiolated coordination polymers (Au CPs) was highlighted. We exclusively emphasize the gold products that are synthesized by the spontaneous interaction of tetrachloroaurate(III) ions (AuCl4¯) with bioligands using amine and thiolate derivatives, including mainly amino acids. The dominant role of the nature of the applied reducing molecules as well as the experimental conditions (concentration of the precursor metal ion, molar ratio of the AuCl4¯ ions and biomolecules; pH, temperature, etc.) of the syntheses on the size and structure-dependent optical properties of these gold nanohybrid materials have been summarized. While using the same reducing and stabilizing biomolecules, the main differences on the preparation conditions of Au NPs, Au NCs, and Au CPs have been interpreted and the reducing capabilities of various amino acids and thiolates have been compared. Moreover, various fabrication routes of thiol-stabilized plasmonic Au NPs, as well as fluorescent Au NCs and self-assembled Au CPs have been presented via the formation of –(Au(I)-SR)n– periodic structures as intermediates.

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7

Ogata, Hideaki, Koji Nishikawa, and Wolfgang Lubitz. "Observation of a metal-hydride in [NiFe] hydrogenase." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C1212. http://dx.doi.org/10.1107/s2053273314087877.

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Hydrogenases catalyze the reversible hydrogen oxidation process by cleaving dihydrogen heterolytically.(1) For this reaction, the enzyme uses the transition metals Ni and Fe, which are abundant in Nature. Standard [NiFe] hydrogenaes are mainly composed of two subunits (total ~90 kDa) The [NiFe] active site is located in the center of the molecule. The active site of [NiFe] hydrogenase is composed of the dinuclear Ni-Fe center, where the Fe ion is coordinated by non-protein ligands (1CO and 2CN¯ ). Two thiolates of cysteine residues are bridging both metals. Furthermore, the Ni is coordinated to the two thiolates of cysteine residues in a terminal fashion. A third bridging ligand is found between the Ni and Fe atom, depending on the redox state.(1) In the inactive form, a third bridging ligand (OH¯¯¯ ) is found between Ni and Fe. Once the enzyme is activated, the bridging position is supposed to be vacant or bridged by a hydride. A previous X-ray crystallographic study at 1.4 Å resolution revealed that the bridging ligand (OH) is removed upon H2 reduction.(2) Electron paramagnetic resonance (EPR) spectroscopy showed that a hydride is located in the bridge between Ni and Fe, which is lost upon illumination at cryogenic temperature.(3) Here we present a crystallographic analysis of the fully reduced (Ni-R) state of [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F at 0.89 Å resolution. The ultra-high resolution analysis revealed the presence of the hydride bridge at the NiFe active site in the catalytically active state. Furthermore the CO and CN ligands could be identified and a protonated thiolate sulfur ligand of the Ni is postulated based on the electron density.

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8

STEPHAN, D. W., and T. T. NADASDI. "ChemInform Abstract: Early Transition-Metal Thiolates." ChemInform 27, no. 28 (August 5, 2010): no. http://dx.doi.org/10.1002/chin.199628302.

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9

Alharthi, Nahed S., Haroon Khan, Fahad Jibran Siyal, Zahid Ali Shaikh, Shumaila Parveen Arain, Lienda Bashier Eltayeb, and Altaf Ali Mangi. "Glutathione, Cysteine, and D-Penicillamine Role in Exchange of Silver Metal from the Albumin Metal Complex." BioMed Research International 2022 (August 8, 2022): 1–10. http://dx.doi.org/10.1155/2022/3619308.

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The purpose of this study is to investigate the exchange reaction taking place among the bovine serum albumin (BSA), 5,5 ′ -dithiobis-(2-nitrobenzoic acid (ESSE), reduced glutathione, N-acetylcysteine, D-penicillamine (thiolates), and silver metal (AgI). For this purpose, stock solutions of BSA and Ellman’s reagent were prepared by dissolving 264 mg of BSA in 5 ml of reaction buffer (0.1 M KH2PO4 at pH 7.8) and 23.8 mg of ESSE in 1.0 ml of reaction buffer which were mixed together. Mixture of BSA-AgI was prepared in a separate procedure by dissolving 0.17 mg of silver nitrate in 1 ml of reaction buffer and then dissolving BSA (200 mg) in the same solution of silver nitrate. Blocking of Cys-34 of BSA with AgI was confirmed by treating different dilutions of BSA-AgI (500 μM) solutions with the solutions of ESSE (85 μM) and ES- (85 μM) and recording the spectra (300-450) with a UV-visible spectrophotometer. The chromatographed AgI-modified BSA ((BSA-S)AgI)) samples (typically 500 μM) were subsequently mixed with thiolates (reduced glutathione, N-acetylcysteine, and D-penicillamine). AgI and modified BSA (typically 500 μM each) were treated with these low molecular weight thiolates and allowed to react overnight followed by chromatographic separation (Sephadex G25). The redox reactions of AgI-modified BSA with various low molecular weight thiols revealed a mechanically important phenomenon. In the case of reduced glutathione and N-acetylcysteine, we observed the rapid release of a commensurate amount of Ellman’s anion, indicating that an exchange has taken place and low molecular weight thiols (RSH) substituted AgI species at the Cys-34 of BSA eventually forming disulfide (BSA-SSR) at Cys-34. It can be anticipated from the phase of study involving bovine serum albumin that low molecular weight thiolates (reduced glutathione and N-acetylcysteine) take off AgI which are attached to proteins elsewhere in the physiological system, making these toxic metals free for toxic action.

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10

Templeton, D. M., P. A. W. Dean, and M. G. Cherian. "The reaction of metallothionein with mercuribenzoate. A dialysis and 113Cd-n.m.r. study." Biochemical Journal 234, no. 3 (March 15, 1986): 685–89. http://dx.doi.org/10.1042/bj2340685.

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Reaction of rat liver cadmium-metallothionein-II(Cd-MT-II) with p-hydroxymercuribenzoate(pHOHgBzO-) causes displacement of bound Cd. When pHOHgBzO- -induced displacement of 109Cd is observed after dialysis of the reaction mixture, the stoichiometry is consistent with stepwise displacement of tetraco-ordinate Cd atoms by non-random entry of reagent into the polynuclear clusters. 113Cd n.m.r. allows direct observation of the effects on bound Cd of stepwise titration of 113Cd-MT-II with pHOHgBzO-. The first equivalent reduces all resonances approximately equally. Subsequently differential reactivity of the protein thiolates towards the reagent gives rise to differential decreases in the 113Cd signal intensities. Resonances previously attributed to a three-metal cluster are lost before those arising from the four-metal cluster. These results are interpreted in terms of current models of the MT structure. They are distinct from the results of reaction of MT with 5,5′-dithiobis-(2-nitrobenzoic acid), which distinguishes between only two classes of thiolates, terminal and bridging. Such different patterns of reactivity of the protein thiolates may underlie a biological activity of this protein.

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11

Petrov, Mikhail L., and Alexander V. Belyakov. "DFT theoretical studies of alkali metal acetylenic thiolates." Tetrahedron Letters 44, no. 3 (January 2003): 599–601. http://dx.doi.org/10.1016/s0040-4039(02)02576-5.

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12

Petrov, M. L., and A. V. Belyakov. "A DFT Study of Acetylenic Alkali Metal Thiolates." Russian Journal of General Chemistry 75, no. 7 (July 2005): 1142–46. http://dx.doi.org/10.1007/s11176-005-0382-z.

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13

Nakamura, A., N. Ueyama, and K. Tatsumi. "Transition metal thiolates: synthetic, catalytic, and biomimetic aspects." Pure and Applied Chemistry 62, no. 6 (January 1, 1990): 1011–20. http://dx.doi.org/10.1351/pac199062061011.

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14

Goitia, Helen, M. Villacampa, Antonio Laguna, and M. Gimeno. "Cytotoxic Gold(I) Complexes with Amidophosphine Ligands Containing Thiophene Moieties." Inorganics 7, no. 2 (January 29, 2019): 13. http://dx.doi.org/10.3390/inorganics7020013.

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A new phosphine ligand bearing a thiophene moiety, C4H3SNHCOCH2CH2PPh2 (L), has been prepared by reaction of the aminophosphine Ph2PCH2CH2NH2 with thiophenecarbonylchloride in the presence of triethylamine. The coordination behavior towards gold(I), gold(III) and silver(I) species has been studied and several metal compounds of different stoichiometry have been achieved, such as [AuL2]OTf, [AuXL] (X = Cl, C6F5), [Au(C6F5)3L], [AgL2]OTf or [Ag(OTf)L]. Additionally, the reactivity of the chloride gold(I) species with biologically relevant thiolates was explored, thus obtaining the neutral thiolate compounds [AuL(SR)] (SR = 2-thiocitosine, 2-thiolpyridine, 2-thiouracil, 2-thionicotinic acid, 2,3,4,6-tetra-6-acetyl-1-thiol-β-d-glucopyranosato or thiopurine). The antitumor activity of the compounds was measured by the MTT method in several cancer cells and the complexes exhibit excellent cytotoxic activity.

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15

Padmos, J. Daniel, David J. Morris, and Peng Zhang. "The structure and bonding properties of tiopronin-protected silver nanoparticles as studied by X-ray absorption spectroscopy." Canadian Journal of Chemistry 96, no. 7 (July 2018): 749–54. http://dx.doi.org/10.1139/cjc-2017-0674.

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Thiolate-protected Ag nanoparticles (NPs) exhibit interesting physical and chemical properties which may lead to various sensing, diagnostic, and therapeutic applications. Further, understanding structure–property relationships of Ag NPs is of great interest to optimize their application. Herein, we used TEM, UV–vis, and a series of synchrotron X-ray spectroscopy techniques to probe the local structure and chemical bonding properties of thiolate-stabilized Ag NPs. Compared with other Ag nanostructures prepared under slightly modified conditions, the Ag NPs were found to have pronounced structural changes, which led to immensely different optical properties. Notably, the NPs were also found to have similar surface structure to recently elucidated Ag nanoclusters prepared with different thiolates. These findings suggest that the NP structure and optical properties can be sensitively tailored by controlling the synthetic conditions. The multi-element, multi-core excitation approach (i.e., Ag K-, Ag L3-, and S K-edges) employed in the X-ray absorption spectroscopy measurements was also demonstrated as an effective tool to uncover the NP structure from both the metal core and the ligand shell perspectives.

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16

Singh, Baljit, and Shavina Shavina. "Direct Electrochemical Synthesis of Nickel (II) Thiolates and their Coordination Complexes." JOURNAL OF ADVANCES IN CHEMISTRY 11, no. 9 (July 29, 2015): 3973–78. http://dx.doi.org/10.24297/jac.v11i9.2688.

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Metallo organic compounds can be synthesized electrochemically by anodic generation of metal cations by using sacrificial metal anode. Bis-thiolates complexes of Nickel, Ni(SR)2 have been prepared in an H-type cell by electrochemical oxidation of thiols RSH (ethanethiol, 2-propanethiol, 1-butanethiol, 1-pentanethiol and thiophenol) with sacrificial Nickel (Ni) anode and inert Platinum (Pt) cathode in non-aqueous solution of acetonitrile containing tetrabutylammonium chloride (as supporting electrolyte). On refluxing with ligand (L) 2,2'-bipyridyl, these thiolates do not form coordination compounds. However, their adducts Ni(SR)2.L have been synthesized electrochemically by adding the ligand to above thiols in solution phase. All these synthesized complexes have been characterized by elemental analysis, infrared spectral data and other physical measurements. All these compounds are in the solid state with excellent yield and associated with high electrochemical efficiency.

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17

Stephan, Hans-Oscar, and Gerald Henkel. "Novel metal thiolates: [Mn2(SC6H3{SiMe3}2)4(C4H8O)], a binuclear manganese thiolate complex with tetrahedral and trigonal-planar metal coordination." Inorganica Chimica Acta 219, no. 1-2 (May 1994): 1–2. http://dx.doi.org/10.1016/0020-1693(94)03839-2.

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18

Busupalli, Balanagulu, Sreenivas Kummara, Guruswamy Kumaraswamy, and Bhagavatula L. V. Prasad. "Ultrathin Sheets of Metal or Metal Sulfide from Molecularly Thin Sheets of Metal Thiolates in Solution." Chemistry of Materials 26, no. 11 (May 23, 2014): 3436–42. http://dx.doi.org/10.1021/cm5006949.

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19

Schenk, Wolfdieter A., and Nikolai Kuhnerta. "Synthesis of Halfsandwich Ruthenium Complexes of Sulfinic Acid Esters [1]." Zeitschrift für Naturforschung B 55, no. 6 (June 1, 2000): 527–35. http://dx.doi.org/10.1515/znb-2000-0614.

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A series of halfsandwich ruthenium sulfinato complexes [CpRu(PR'3)2(SO2R)] (R = Me, CH2Ph, C2H4Ph, Ph, 4-C6H4Me; PR'3 = PMe3, 1/2 dppm) with various electronic and steric environments around the ruthenium centre, have been prepared by insertion of SO2 into a ruthenium carbon bond, by a direct ligand exchange reaction, or by oxidation of thiolato complexes with 3-chloroperoxybenzoic acid. The chiral complexes [CpRu(CO )(PPh3)(SO2R)] (R = Me, CH2Ph, Ph) were obtained similarly by oxidation of the corresponding thiolates with magnesium monoperoxyphthalate. Alkylation of the sulfinato complexes with oxonium salts [R"3O]X (R" = Me, Et; X = BF4 , PF6) gave ruthenium complexes of sulfinic acid esters, [CpRu(L)(L′)(S(O)(OR″)R)]X in high yields and, for the chiral complexes, up to 82% de. The esters may be detached from the metal by ligand exchange with acetonitrile. Stronger nucleophiles such as I- or SMe- dealkylate the coordinated sulfinic acid esters.

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20

Zhang, Dong, Billy Hernandez, and Matthias Selke. "Photooxidation of metal-bound thiolates: reactivity of sulfur containing peroxidic intermediates." Journal of Sulfur Chemistry 29, no. 3-4 (August 1, 2008): 377–88. http://dx.doi.org/10.1080/17415990802146980.

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21

Odriozola, Ibon, Nerea Ormategui, Iraida Loinaz, José A. Pomposo, and Hans J. Grande. "Coinage Metal–Glutathione Thiolates as a New Class of Supramolecular Hydrogelators." Macromolecular Symposia 266, no. 1 (June 2008): 96–100. http://dx.doi.org/10.1002/masy.200850618.

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22

Guan, Zong-Jie, Jiu-Lian Zeng, Zi-Ang Nan, Xian-Kai Wan, Yu-Mei Lin, and Quan-Ming Wang. "Thiacalix[4]arene: New protection for metal nanoclusters." Science Advances 2, no. 8 (August 2016): e1600323. http://dx.doi.org/10.1126/sciadv.1600323.

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Surface organic ligands are critical for the formation and properties of atomically precise metal nanoclusters. In contrast to the conventionally used protective ligands such as thiolates and phosphines, thiacalix[4]arene has been used in the synthesis of a silver nanocluster, [Ag35(H2L)2(L)(C≡CBut)16](SbF6)3, (H4L, p-tert-butylthiacalix[4]-arene). This is the first structurally determined calixarene-protected metal nanocluster. The chelating and macrocyclic effects make the thiacalix[4]arene a rigid shell that protects the silver core. Upon addition or removal of one silver atom, the Ag35 cluster can be transformed to Ag36 or Ag34 species, and the optical properties are changed accordingly. The successful use of thiacalixarene in the synthesis of well-defined silver nanoclusters suggests a bright future for metal nanoclusters protected by macrocyclic ligands.

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23

Souza, Maykon Lima, Antonio Carlos Roveda, José Clayston Melo Pereira, and Douglas Wagner Franco. "New perspectives on the reactions of metal nitrosyls with thiolates as nucleophiles." Coordination Chemistry Reviews 306 (January 2016): 615–27. http://dx.doi.org/10.1016/j.ccr.2015.03.008.

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24

Chadwick, Scott, Ulrich Englich, Karin Ruhlandt-Senge, Charles Watson, Alice E. Bruce, and Mitchell R. M. Bruce. "Formation of separated versus contact ion pairs in alkali metal thiolates and selenolates." Journal of the Chemical Society, Dalton Transactions, no. 13 (2000): 2167–73. http://dx.doi.org/10.1039/b000665n.

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25

Vericat, C., M. E. Vela, G. Corthey, E. Pensa, E. Cortés, M. H. Fonticelli, F. Ibañez, G. E. Benitez, P. Carro, and R. C. Salvarezza. "Self-assembled monolayers of thiolates on metals: a review article on sulfur-metal chemistry and surface structures." RSC Adv. 4, no. 53 (2014): 27730–54. http://dx.doi.org/10.1039/c4ra04659e.

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26

Liebeskind, Lanny S., Jiri Srogl, Cecile Savarin, and Concepcion Polanco. "Bioinspired organometallic chemistry." Pure and Applied Chemistry 74, no. 1 (January 1, 2002): 115–22. http://dx.doi.org/10.1351/pac200274010115.

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Given the stability of the bond between a mercaptide ligand and various redox-active metals, it is of interest that Nature has evolved significant metalloenzymatic processes that involve key interactions of sulfur-containing functionalities with metals such as Ni, Co, Cu, and Fe. From a chemical perspective, it is striking that these metals can function as robust biocatalysts in vivo, even though they are often "poisoned" as catalysts in vitro through formation of refractory metal thiolates. Insight into the nature of this chemical discrepancy is under study in order to open new procedures in synthetic organic and organometallic chemistry.

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27

Dance, IG, PJ Guerney, AD Rae, ML Scudder, and AT Baker. "Metal-Complexes of Thiocholinate, -SCH2CH2Nme3+. I. Preparation and Crystal-Structure of Pentakis(Thiocholinato)Dilead(II) Hexafluorophosphate." Australian Journal of Chemistry 39, no. 3 (1986): 383. http://dx.doi.org/10.1071/ch9860383.

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Aqueous solutions containing lead(II) and deprotonated thiocholine contain water-soluble homoleptic lead thiolates , which crystallize as yellow needles of [Pb2(SCH2CH2NMe3)5] (PF6)4 in the presence of PF6-, but crystallize [ Pb (SCH2CH2NMe3)2](ClO4)2 with 1 : 2 stoichiometry in the presence of ClO4-. Crystalline [Pb2(SCH2CH2NMe3)5](PF6)4 contains almost linear chains composed of end-linked {(SR)2Pb(μ-SR) Pb (SR)2} coordination units, within which the primary Pb -S coordination (mean 2.73 Ǻ, sample e.s.d . 0.10 Ǻ) is orthogonal trigonal (S- Pb -S, mean 88.9°, sample e.s.d .3.7°) at each lead atom. Within the {Pb2(SR)5} unit there is one double bridge with two rimary bonds, and one double bridge involving one secondary Pb --S connection (mean 3.23 Ǻ, sample e.s.d . 0.12 Ǻ). Three double-bridges involving secondary Pb --S coordination link the ends of the dimetallic units, and consequently bis - and tris -double thiolate bridges alternate along the chain. Overall coordination at each lead atom is pseudo-octahedral, with one non-bonding electron pair and two cis secondary Pb --S bonds. The cationic tails of the ligands radiate from the chains into a matrix of PF6- ions, and the chains are approximately hexagonally close-packed with a separation of 14.4 Ǻ. Along the b axis there are homogeneous stacks of the ammonium functions, the anions, and the Pb, S chains, with a pseudo-symmetric repeat of b/3 in each stack, allowing disorder due to stacking faults. This disorder has been adequately modelled in the refinement, which also incorporated back-Fourier-transform techniques to avoid inaccuracies due to spherically disordered PF6- ions. Crystal data: Cc, 25.535(8), b 43.13(1), c 15.123(5)Ǻ, β 100.36(9)°, Z 12 (× Pb2S5C25H65N5P4F24), 3585 observed data, R 0.066.

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28

Baranano, David, Grace Mann, and John F. Hartwig. "Nickel and Palladium-Catalyzed Cross-Couplings that Form Carbon-Heteroatom and Carbon-Element Bonds." Current Organic Chemistry 1, no. 3 (September 1997): 287–305. http://dx.doi.org/10.2174/1385272801666220124194647.

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The transition-metal catalyzed addition of heteroatom nucleophiles to aryl and vinyl halides is reviewed. This chemistry typically involves a nickel- or palladium-based catalyst containing phosphine ligands. In recently developed palladium-catalyzed chemistry, aryl halides react with amines in the presence of base to form arylamines. In similar chemistry catalyzed by both nickel and palladium, aryl and vinyl halides react with alkali metal or tin thiolates or selenides to form aryl and vinyl sulfides, while the reaction of different phosphorus compounds, such as phosphides, phosphonates, and phosphonites, with aryl halides gives compounds with new aryl-p· linkages. In addition to these typically nucleophilic heteroatoms, electrophilic heteroatoms such as boron, silicon, tin, and germanium have also been coupled to aryl electrophiles. The review closes with a brief summary of the general reaction pathways of these C-X bond-forming processes.

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29

Sellmann, Dieter, Wolfgang Kern, Adelgunde Holzmeier, Georg Pöhlmann, and Matthias Moll. "Übergangsmetallkomplexe mit Schwefelliganden, LXVI / Transition Metal Complexes with Sulfur Ligands, LXVI." Zeitschrift für Naturforschung B 46, no. 10 (October 1, 1991): 1349–56. http://dx.doi.org/10.1515/znb-1991-1013.

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Since substrate addition and elimination reactions are essential reactions of metal sulfur centres in oxidoreductases, we investigated the substitution of chloride in [Mo(Cl)(NO)(′S4')](1) (′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-)) [4] and in the analogous tungsten complex [W(Cl)(NO)(′S4')](2). The chloride ligands in 1 and 2 can easily be substituted by thiolates to give [M(SR)(NO)(′S4')] (M = Mo, R = Me 3a,′Pr 3b, nBu 3c, Ph 3d; M = W, R = Me 4a, Ph 4b). For these substitution reactions an associative mechanism is suggested. The SR- ligands act probably as σ-π four electron donor ligands to give metal centres with an 18 electron configuration as also found in the amido complexes [Mo(NR2)(NO)('S4')] [4]. 1 and 2 react with PMe3 to yield the adducts [M(PMe3)(Cl)(NO)('S4')] (M = Mo 5, W 6), whose NMR spectra indicate the formation of two stereoisomers in a ratio of about 2:3.

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30

Wang, Long-Sheng, Tian-Lu Sheng, Xin Wang, Dong-Bo Chen, Sheng-Min Hu, Rui-Biao Fu, Sheng-Chang Xiang, and Xin-Tao Wu. "Self-Assembly of Luminescent Sn(IV)/Cu/S Clusters Using Metal Thiolates as Metalloligands." Inorganic Chemistry 47, no. 10 (May 2008): 4054–59. http://dx.doi.org/10.1021/ic701741m.

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31

Kang, Bei-sheng, Mao-chun Hong, Ting-bin Wen, Han-qin Liu, and Jia-xi Lu. "Transition metal 1,2-bidentate thiolates as building blocks and their construction into cluster complexes." Journal of Cluster Science 6, no. 3 (September 1995): 379–401. http://dx.doi.org/10.1007/bf01165468.

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32

Henkel, Gerald, and Stefan Weissgräber. "Novel Metal Thiolates:[Co2(SC3H7)5]−, the First Complex with Face-Sharing MS4 Tetrahedra." Angewandte Chemie International Edition in English 31, no. 10 (October 1992): 1368–69. http://dx.doi.org/10.1002/anie.199213681.

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33

Chadwick, Scott, and Karin Ruhlandt-Senge. "The Remarkable Structural Diversity of Alkali Metal Pyridine-2-thiolates with Mismatched Crown Ethers." Chemistry - A European Journal 4, no. 9 (September 4, 1998): 1768–80. http://dx.doi.org/10.1002/(sici)1521-3765(19980904)4:9<1768::aid-chem1768>3.0.co;2-j.

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34

Chadha, Raj K., Rajesh Kumar, Jaime Romero Lopez-Grado, and Dennis G. Tuck. "The direct electrochemical synthesis of thiolato complexes of cobalt and nickel, and the crystal structure of bis(phenylthiolato)bis(1,10-phenanthroline)cobalt(III) perchlorate." Canadian Journal of Chemistry 66, no. 9 (September 1, 1988): 2151–56. http://dx.doi.org/10.1139/v88-341.

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Cobalt(II) and nickel(II) thiolates, M(SR)2, can be prepared in high yield by the electrochemical oxidation of a metal anode in an acetonitrile or acetone solution of RSH (R = C6H5, o-CH3C6H4, 2-C10H7, 2,3,4,5-C6F4H; not all combinations). When 2,2-bipyridine or 1,10-phenanthroline (=L) is added to the electrolyte phase, the products are the adducts M(SR)2L2. In the case of Co(SC6H5)2(phen)2, aerial oxidation leads to the formation of the cobalt(III) cation [Co(SC6H5)2(phen)2]+, isolated as the perchlorate salt. X-ray crystallographic analysis showed that this cation has a cis-CoS2(N2)2 kernel.

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35

Smith, Doris A., Botao Zhuang, William E. Newton, John W. McDonald, and Franklin A. Shultz. "Two-electron transfer accompanied by metal-metal bond formation. Synthesis and electrochemistry of dinuclear molybdenum and tungsten carbonyl thiolates." Inorganic Chemistry 26, no. 15 (July 1987): 2524–31. http://dx.doi.org/10.1021/ic00262a036.

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36

Golden, Melissa L., Jason C. Yarbrough, Joseph H. Reibenspies, and Marcetta Y. Darensbourg. "Sensing of Sulfur Dioxide by Base Metal Thiolates: Structures and Properties of Molecular NiN2S2/SO2Adducts." Inorganic Chemistry 43, no. 15 (July 2004): 4702–7. http://dx.doi.org/10.1021/ic049387n.

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37

Harding, Marjorie M. "The geometry of metal–ligand interactions relevant to proteins." Acta Crystallographica Section D Biological Crystallography 55, no. 8 (August 1, 1999): 1432–43. http://dx.doi.org/10.1107/s0907444999007374.

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Geometrical data which could be of relevance in the structure determination, structure refinement, assessment or understanding of metalloproteins have been extracted from the Cambridge Structural Database (CSD). The CSD contains crystallographic data from `small-molecule' structures determined by X-ray or neutron diffraction to an accuracy much better than that of most current protein structure determinations. The structures selected have a crystallographic R factor ≤ 0.065 and contain Ca, Mg, Mn, Fe, Cu or Zn interacting with ligands which are analogues of the amino-acid side chains commonly found in proteins; they include carboxylate groups, alcohols, phenolates, thiolates, imidazole groups and also water molecules. For each pair, the mean metal–donor-atom distance, the sample standard deviation and the range of observed values are tabulated, using ∼4500 observations in all. Where practicable, subsets with different coordination numbers and/or oxidation states are given. Also included are inter-bond angles at the ligand donor atom, the orientation of carboxylate and imidazole groups with respect to the metal–donor-atom bond and some other aspects of ligand geometry. Thus, for example, target distances and their standard deviations could be easily looked up for the validation of a metalloprotein structure or for use in restrained refinement with low-resolution data.

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38

KANG, B., M. HONG, T. WEN, H. LIU, and J. LU. "ChemInform Abstract: Transition Metal 1,2-Bidentate Thiolates as Building Blocks and Their Construction into Cluster Complexes." ChemInform 27, no. 7 (August 12, 2010): no. http://dx.doi.org/10.1002/chin.199607283.

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39

Krebs, Bernt, and Gerald Henkel. "Transition-Metal Thiolates: From Molecular Fragments of Sulfidic Solids to Models for Active Centers in Biomolecules." Angewandte Chemie International Edition in English 30, no. 7 (July 1991): 769–88. http://dx.doi.org/10.1002/anie.199107691.

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40

Krężel, Artur, and Wolfgang Maret. "Different redox states of metallothionein/thionein in biological tissue." Biochemical Journal 402, no. 3 (February 26, 2007): 551–58. http://dx.doi.org/10.1042/bj20061044.

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Mammalian metallothioneins are redox-active metalloproteins. In the case of zinc metallothioneins, the redox activity resides in the cysteine sulfur ligands of zinc. Oxidation releases zinc, whereas reduction re-generates zinc-binding capacity. Attempts to demonstrate the presence of the apoprotein (thionein) and the oxidized protein (thionin) in tissues posed tremendous analytical challenges. One emerging strategy is differential chemical modification of cysteine residues in the protein. Chemical modification distinguishes three states of the cysteine ligands (reduced, oxidized and metal-bound) based on (i) quenched reactivity of the thiolates when bound to metal ions and restoration of thiol reactivity in the presence of metal-ion-chelating agents, and (ii) modification of free thiols with alkylating agents and subsequent reduction of disulfides to yield reactive thiols. Under normal physiological conditions, metallothionein exists in three states in rat liver and in cell lines. Ras-mediated oncogenic transformation of normal HOSE (human ovarian surface epithelial) cells induces oxidative stress and increases the amount of thionin and the availability of cellular zinc. These experiments support the notion that metallothionein is a dynamic protein in terms of its redox state and metal content and functions at a juncture of redox and zinc metabolism. Thus redox control of zinc availability from this protein establishes multiple methods of zinc-dependent cellular regulation, while the presence of both oxidized and reduced states of the apoprotein suggest that they serve as a redox couple, the generation of which is controlled by metal ion release from metallothionein.

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41

Springfield, Elliot, Alana Willis, John Merle, Johanna Mazlo, and Maria Ngu-Schwemlein. "Spectroscopic and Theoretical Studies of Hg(II) Complexation with Some Dicysteinyl Tetrapeptides." Bioinorganic Chemistry and Applications 2021 (July 23, 2021): 1–12. http://dx.doi.org/10.1155/2021/9911474.

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Tetrapeptides containing a Cys-Gly-Cys motif and a propensity to adopt a reverse-turn structure were synthesized to evaluate how O-, N-, H-, and aromatic π donor groups might contribute to mercury(II) complex formation. Tetrapeptides Xaa-Cys-Gly-Cys, where Xaa is glycine, glutamate, histidine, or tryptophan, were prepared and reacted with mercury(II) chloride. Their complexation with mercury(II) was studied by spectroscopic methods and computational modeling. UV-vis studies confirmed that mercury(II) binds to the cysteinyl thiolates as indicated by characteristic ligand-to-metal-charge-transfer transitions for bisthiolated S-Hg-S complexes, which correspond to 1 : 1 mercury-peptide complex formation. ESI-MS data also showed dominant 1 : 1 mercury-peptide adducts that are consistent with double deprotonations from the cysteinyl thiols to form thiolates. These complexes exhibited a strong positive circular dichroism band at 210 nm and a negative band at 193 nm, indicating that these peptides adopted a β-turn structure after binding mercury(II). Theoretical studies confirmed that optimized 1 : 1 mercury-peptide complexes adopt β-turns stabilized by intramolecular hydrogen bonds. These optimized structures also illustrate how specific N-terminal side-chain donor groups can assume intramolecular interactions and contribute to complex stability. Fluorescence quenching results provided supporting data that the indole donor group could interact with the coordinated mercury. The results from this study indicate that N-terminal side-chain residues containing carboxylate, imidazole, or indole groups can participate in stabilizing dithiolated mercury(II) complexes. These structural insights on peripheral mercury-peptide interactions provide additional understanding of the chemistry of mercury(II) with side-chain donor groups in peptides.

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42

Brines, Lisa M., Gloria Villar-Acevedo, Terutaka Kitagawa, Rodney D. Swartz, Priscilla Lugo-Mas, Werner Kaminsky, Jason B. Benedict, and Julie A. Kovacs. "Comparison of structurally-related alkoxide, amine, and thiolate-ligated MII (M=Fe, Co) complexes: The influence of thiolates on the properties of biologically relevant metal complexes." Inorganica Chimica Acta 361, no. 4 (March 2008): 1070–78. http://dx.doi.org/10.1016/j.ica.2007.07.038.

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43

El-khateeb, Mohammad, Khaled Shawakfeh, Mazen Al-Btoosh, Helmar Görls, and Wolfgang Weigand. "Synthesis of cyclopentadienyl ruthenium 4-pyridine and 2-pyrimidine thiolates and their bimetallic group VI metal carbonyls." Polyhedron 89 (March 2015): 70–75. http://dx.doi.org/10.1016/j.poly.2014.12.037.

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44

C̣etinkaya, Bekir, Peter B. Hitchcock, Michael F. Lappert, and Richard G. Smith. "The first neutral, mononuclear 4f metal thiolates and new methods for corresponding aryl oxides and bis(trimethylsilyl)amides." J. Chem. Soc., Chem. Commun., no. 13 (1992): 932–34. http://dx.doi.org/10.1039/c39920000932.

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45

Power, Philip P., and Steven C. Shoner. "The Neutral Transition Metal Thiolates[M(SAr)2]2(M Mn, Fe or Co, Ar 2,4,6-t-Bu3C6H2)." Angewandte Chemie International Edition in English 30, no. 3 (March 1991): 330–32. http://dx.doi.org/10.1002/anie.199103301.

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46

Krüger, Thomas, Bernt Krebs, and Gerald Henkel. "[Ni4(SC3H7)8Br] and[Ni4(SC3H7)8I]: Mixed Valent Nickel Thiolates with Integral and Nonintegral Metal Oxidation States." Angewandte Chemie International Edition in English 31, no. 1 (January 1992): 54–56. http://dx.doi.org/10.1002/anie.199200541.

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47

Das, Ujjwal. "Platinum Group Metals Bonded Thiolato Sulfur Oxygenation: Photoactivity and Bioactivity." Asian Journal of Chemistry 34, no. 12 (2022): 3059–70. http://dx.doi.org/10.14233/ajchem.2022.24007.

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Platinum group metals mediated thiolato compounds are highly susceptible for S-centered reactivity owing to high nucleophilicity and which is enormously significant in the point of its bioactivity and photoactivity. A series of oxygenation reactions of thiolate sulfur attached with platinum metals occurred with molecular O2 in varying conditions. A variety of sulfenates and sulfinates are produced depending on nature of starting substrate thiolato and the oxygenations are facile under harshly oxygen environment. There are numerous mechanistic paths for the oxygenation of platinum metals bonded thiolate S-center unlike the oxygenation reaction of organic sulphides. It is assumed that S-oxygenation occurs via the intramolecular and intermolecular dioxygen addition pathways. A number of mysterious photo-induced sulphur oxygenation and self-sensitization reactions of metal-thiolato to analogous oxygenate are also mentioned. These compounds show enzymatic catalytic activity and remarkable bioactivity also interaction with the biomolecules like DNA, which opens a new area for the researchers for designing novel heavier metals-sulfur-oxygenates compounds as metallodrugs.

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48

Weigand, Wolfgang, Michael Weishäupl, and Christian Robl. "Metallkomplexe mit funktionalisierten Schwefelliganden, X [1] Ruthenium(II)-und Platin(II)-1-alkin-1-thiolato-Komplexe. Kristallstrukturanalyse von trans-(Ph3P)2Pt[S-C≡C-C(CH3)3]2 / Metal Complexes of Functionalized Sulfur Containing Ligands, X [1] Synthesis of Ruthenium (II) and Platinum(II) 1-Alkyne-1-thiolato Complexes. X-Ray Structure Analysis of trans-( Ph3P)2Pt[C-C≡C-C(CH3)3]2." Zeitschrift für Naturforschung B 51, no. 4 (April 1, 1996): 501–5. http://dx.doi.org/10.1515/znb-1996-0412.

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Abstract The 1-alkyne-1-thiolates R-C ≡C-SLi [1a: R = C(CH3)3, 1b: R = C6H11 ] react with L2PtCl2 (L = PPh3, 1/2 dppe) and CpRu(PPh3)2Cl, respectively to give the complexes trans-(Ph3P)2Pt[S-C ≡C-C(CH3)3]2 (2a), cis-dppePt[S-C≡C-C(CH3)3]2 (2b), and CpRu(PPh3)2-(S-C ≡ C-R) [3a: R = C(CH3)3, 3b: R = C6H11]. 2a has been characterized by 31P CP/MAS NM R spectroscopy and its crystal structure determined by X-ray diffraction.

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49

Niemeyer, Mark, and Philip P. Power. "Donor-Free Alkali Metal Thiolates: Synthesis and Structure of Dimeric, Trimeric, and Tetrameric Complexes with Sterically Encumbered Terphenyl Substituents." Inorganic Chemistry 35, no. 25 (January 1996): 7264–72. http://dx.doi.org/10.1021/ic960570t.

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50

Wilker, Jonathan J., and Stephen J. Lippard. "Alkyl Transfer to Metal Thiolates: Kinetics, Active Species Identification, and Relevance to the DNA Methyl Phosphotriester Repair Center ofEscherichiacoliAda." Inorganic Chemistry 36, no. 6 (March 1997): 969–78. http://dx.doi.org/10.1021/ic961082o.

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