Dithio Complexes Research Articles

Synthesis, Spectral and Antimicrobial Studies of Bis (Cyclopentadienyl) Titanium (IV) Bis (O,O’-Dialkyl and Alkylenedithiophosphate) Complexes

A new complexes of Cp2Ti[S2P(OR)2]2 (where R = Et, Pr-n, Pr-i, Bu-i and Ph) and Cp2Ti[S2POGO]2 (where G = -CH2CMe2CH2-, -CH2CEt2CH2- and -CMe2CMe2-) were prepared by the dropwise addition of the appropriate O,O’-dialkyl or -alkylenedithiophosphoric acid to biscyclopentadienyl titanium dichloride in 1:2 molar ratio and refluxed in benzene solution. These novel deep red colored complexes were characterized by elemental analyses, molecular weight measurements and spectroscopic techniques (IR., NMR 1H, 13C and 31P NMR). These titanium (IV) dithio complexes have also been screened for their antibacterial activities.

Self assembly of homoleptic Ni(ii) dithiocarbamates and dithiocarbimates via Ni⋯H–C anagostic and C–H⋯π (chelate) interactions

New homoleptic complexes of the form [Ni(L)2] (L = L1 (dibenzyl dithiocarbamate) 1, L2 (N-benzyl-N,N-dimethyl ethylene dithiocarbamate) 2, and (R)2[Ni(L3)2)] (L3 = p-chlorobenzene sulfonyl dithiocarbimate; R = (C2H5)4N+3, (C3H7)4N+4, (C6H13)4N+5) have been prepared and characterized by elemental analyses, IR, 1H and 13C NMR and UV-visible absorption spectra. In addition, their structures have been elucidated by X-ray crystallography. The crystal structure of 1 reveals unusual C–H⋯Ni intermolecular anagostic interactions in axial positions resulting in 1D supramolecular chains, whereas complex salts 3 and 5 display unique C–H⋯Ni anagostic interactions due to the close proximity of one or two methylene protons in the cationic moieties to the Ni(II) center of the [Ni(L3)2]2− complex anion, providing pseudo-square pyramidal and octahedral coordination environments respectively about the metal centers. To the best of our knowledge, 3 and 5 are the first examples of inter-ionic anagostic interactions within dithio complexes. Theoretical calculations have been performed for 3 and 5. The energy of interaction for 3 and 5 was found to be more than the previously reported neutral complexes. The supramolecular networks in all the complexes are sustained by non-conventional C–H⋯O, C–H⋯N and C–H⋯π (chelate, NiS2C) bonding interactions. All complexes are weakly conducting with σrt ∼10−6 S cm−1.

Unusual C–H⋯Ni anagostic interactions in new homoleptic Ni(ii) dithio complexes

Six new homoleptic complexes of the general form [Ni(L2)] [L = L1 (9-fluorenylmethyl)xanthate (1); L2 (cyclobutylmethyl)xanthate (2); L3 (1-benzyl-4-hydroxypiperidine)xanthate (3); L4 (N-benzyl-N-methylpyridyl)dithiocarbamate (4); L5 (N-methylfuryl-N-methylpyridyl)dithiocarbamate (5); L6 (N-benzyl-N-methylfuryl)dithiocarbamate (6)] have been prepared and characterized by microanalysis, spectroscopy (IR, 1H and 13C NMR, UV-Vis) and their structures have been elucidated by X-ray crystallography. In all complexes the metals are four coordinate with square planar coordination geometries although in the crystal structures of 2 and 4 significant C–H⋯Ni anagostic intermolecular interactions in axial positions are found which involve the metal atom in chain motifs. As far as we are aware 2 and 4 are unique examples of homoleptic metal dithio complexes exhibiting such type of anagostic interactions. In the remaining complexes (1, 3, 5 and 6) supramolecular frameworks are stabilised by S⋯S, C–H⋯S, C–H⋯π and π⋯π non-covalent interactions. All six complexes are weakly conducting (σrt = 10−11–10−8 S cm−1; Ea = 0.37–1.40 eV) and show semiconductor behaviour in the 303–393 K temperature range.

Syntheses, crystal and molecular structures, and properties of some new phenylmercury(ii) dithiolate complexes

A series of new phenylmercury(II) dithio complexes [PhHg(Bun2dtc)] (; Bun2dtc-=di-n-butyldithiocarbamate), [PhHg(morphdtc)] (; morphdtc-=morpholinedithiocarbamate), [PhHg(Bz2dtc)] (; Bz2dtc-=dibenzyldithiocarbamate), [PhHg(methoxethxant)] (; methoxethxant-=2-methoxyethylxanthate) [(PhHg)2NED] (; NED2-=1-nitroethylene-2,2-dithiolate) and [(PhHg)2CDC] (; CDC2-=cyanodithioimidocarbonate) have been prepared and characterized by elemental analysis, UV-Vis, IR, 1H and 13C NMR spectra and mass spectrometry. The crystal structures of , and showed a linear Hg(II) core at the center of the molecules. The weak intra- and intermolecular HgS interactions provide a molecular chain framework. The reaction of PhHgO2CCH3 with Bun2dtcH gave the known dimeric complex Hg(Bun2dtc)2 while the Ni(O2CCH3)2 mediated reaction gave instead of the expected heterobimetallic complex [PhHgNi(Bun2CS2)2]O2CCH3 which has been corroborated by natural charges at each atom obtained at the density functional level (DFT) of theory. Upon excitation at 358 nm exhibited a medium strong photoluminescence emission at 420 nm as a consequence of intraligand pi-->pi* transitions. The electronic absorption bands of were assigned from time dependent density functional theory (TD-DFT) calculations. Geometrical configurations of , and have been optimized using the DFT method. All of the complexes are weakly conducting (sigmart approximately 10(-12) S cm(-1)). However and exhibited semiconductivity with band gaps of 0.39 and 0.94 eV respectively.

Synthesis, structural aspects and ligation behaviour of phenylmercury(II) dithio complexes having Hg-S bonds

: Reactions of C 6 H 5 HgOH with CS 2 and 2-alkyl amino ethanol at -20 °C yield neutral two coordinate unsymmetrically substituted phenylmercury(n) N-alkyl, N-hydroxyethyl dithiocarbamate complexes, [C 6 H 5 HgS(S)-CN(R)CH 2 CH 2 OH] [R =CH 3 (1), C 2 H 5 (2), n-C 4 H 9 (3)]. Few bimetallic derivatives of compound 1 and 2 with Hg, Cd and Ag I salts have also been prepared. The products have been characterised using analytical and spectroscopic (IR, UV, 1 H and 13 C NMR) data. The bimetallic adducts 4-13 are formed through the coordination of the sulfur atom of phenylmercury(ll) N-alkyl, N-hydroxyethyl dithiocarbamate to the soft metal acceptors.

Preparation, spectroscopic investigation and antibacterial activity of some organomercury(II) and organotin(IV) dithio complexes

Phenylmercuric acetate, triphenyltin chloride and dibutyltin chloride react with alkali-metal or ammonium salts of some 1,1- and 1,2-dithio ligands in appropriate molar ratios to yield a series of organometallic dithio complexes of the type [PhHgX] (X = butylxanthate (Buxant−), cyclohexylxanthate (Cyxant−), benzylxanthate (Bzxant−) or pyrrolidin-1-yldithiocarbamate (Pdtc−); [(PhHg)2X] (X = isomaleonitriledithiolate (i-MNT2−) or 1-ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate (ecda2−); Ph3SnX (X = Buxant− or Pdtc−); [(Ph3Sn)2(i-MNT)] and [Bu2SnMNT] (MNT2− = maleonitriledithiolate). These complexes have been characterized by elemental analysis, molar conductance measurements, IR, FT-Raman, 1H and 13C NMR and fast atom bombardment (FAB) mass spectra. Cyclic dimeric structures for phenylmercuryxanthates and monomeric structures for the remaining complexes are suggested. Antibacterial activities of the complexes and parent ligands have been screened against some well-known pathogenic bacteria. Organomercury dithiolates have been found to be more potential antibacterial than organotin complexes. Copyright © 2000 John Wiley & Sons, Ltd.

Synthesis and spectral studies of some new palladium(II) and platinum(II) dithio complexes: The novel crystal structure of the palladium(II) dithiocarbimato complex

A new 4-aminophenyl ammonium dithiocarbamate ligand and its Pd II and Pt II complexes have been synthesized and characterized by analytical, magnetic and spectroscopic techniques. These complexes on reaction with strong base form novel anionic metal(II) dithiocarbimates, which have also been isolated and studied. The spectroscopic and magnetic data clearly indicate the bidentate bonding by the dithiocarbamate ligand in the complexes and which have square planar configurations. The single-crystal X-ray analysis of (Bu 4 nN) 2[Pd(S 2CNC 6H 4NH 2) 2] gave the first example of the structure of a dithiocarbimato complex. The Pd II complex has a square-planar configuration with the S 2CNC 6H 4NH 2 group coordinated as an asymmetric bidentate ligand forming a stable four-membered ring by chelation through the two sulfur atoms.

Characterization of Cure Profile of Anaerobic Adhesives by Real-Time FT-IR Spectroscopy. I. Effect of Transition Metal Dithiolate Complexes

Abstract A model acrylic adhesive formulation consisting of triethylene glycol dimethacrylate (TRIEGMA) monomer, cumene hydroperoxide (CHP), o-benzoic sulfimide (saccharin or BS) and with or without a metal dithiolate catalyst has been made to study kinetics and mechanism of the anaerobic polymerization. In these studies, a real-time FT-IR spectroscopic (RT/FT-IR) technique has been used to study anaerobic cure profiles at room temperature. The catalytic effect of several transition metal dithio complexes for redox-initiated acrylate polymerization has been studied. The dithiolates used in these studies include the dithiocarbamate, xanthate dithiophosphate complexes of copper, nickel and zinc systems. Copper diacetylacetonate was also studied for comparison of its catalytic reactivity. A syner-gistic effect of copper dithiolate catalyst and saccharin was observed. The effects of catalyst concentration, metal and ligand type, and co-initiator on cure profiles have been monitored in a real-time mode.

Phenylmercury Dithio Complexes as Ligands: Preparation and Spectroscopic Characterization of Heterobimetallic Complexes Obtained from Bisdithio Complexes of Ni(II), Pd(II), and Pt(II) as Lewis Acids

Abstract Reaction of PhHgX [X=ethylxanthate (xant) or N,N′-diethyldithiocarbamate (dtc)] with MX2 [M=Ni(II), Pd(II) or Pt(II)] occurs, to afford a new class of golden green to yellowish brown organo heterobimetallic complexes, PhHgXMX2 with MS4 coordination geometry. The precursor PhHgX, have also been characterized. All the complexes are quite stable in solid and solution and are non-conducting species. In PhHgX, IR and NMR spectral studies suggest that dithio ligands are bound to phenylmercury in a linear fashion with additional Hg···S linkage in monodentate manner. Diamagnetism and electronic spectra indicate square planar geometry around M(II) in all the heterobimetallic complexes. IR and NMR spectral studies suggest the presence of monodentate and symmetrical bidentate dithio groups in heterobimetallic complexes.

ChemInform Abstract: Electronic Ground States, Chemical Reactivity, and Related Properties of Square‐Planar Platinum(II) Dithio Complexes.

AbstractEHMO‐SCCC calculations are carried out on four model Pt(II) complexes of the type (I)‐(IV).

Electronic ground states, chemical reactivity, and related properties of square-planar platinum(II) dithio complexes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTElectronic ground states, chemical reactivity, and related properties of square-planar platinum(II) dithio complexesEvangelos G. Bakalbassis, George A. Katsoulos, and Constantinos A. TsipisCite this: Inorg. Chem. 1987, 26, 19, 3151–3158Publication Date (Print):September 1, 1987Publication History Published online1 May 2002Published inissue 1 September 1987https://doi.org/10.1021/ic00266a018RIGHTS & PERMISSIONSArticle Views64Altmetric-Citations27LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (909 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

A unidentate difluorodithiophosphate complex and a synthetic study of some dithio complexes

A unidentate difluorodithiophosphate complex and a synthetic study of some dithio complexes