Gold(I) complexes with thiolate and triphenylphosphine ligands

The reaction of [AuCl(PPh₃)] with Pb(SR)₂(R = C₂H₅, C₆H₅, CH₂C₆H₅, C₆F₅, C₆H₂Me₃-2,4,6, Prⁱ and Bu^t) provides a clean method to obtain complexes of the type [Au(SR)(PPh₃)] in good yields. The new compounds have been characterized by IR, ¹H, ³¹P, ¹⁹F and ³¹C NMR. A study by FAB mass spectrometry indicates that an ion-molecule aggregation process takes place.     

Mononuclear tungsten(VI) complexes with bis(phenolato) ligands: syntheses,characterisations and activity in ROMP reaction

The reaction of bulky ligand precursor 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (H₂mbp) or 2,2′-ethylidenebis(4,6-di-tert-butylphenol) (H₂ebp) with trisdiolatotungsten(VI) complex [W(eg)₃] 1 (eg=ethanediolate dianion) provides heteroleptic complexes [W(mbp)(eg)₂] 2 or [W(ebp)(eg)₂] 3, respectively. Sterically less hindered 2,2′-dihydroxy-1,1′-dinaphtylmethane (H₂dinap) forms heteroleptic disubstituted complex [W(dinap)₂(eg)] 4. The X-ray crystal structure determinations confirmed that the isolated compounds are made of monomeric tris(diolato)tungsten(VI) molecules in which the central tungsten atom is bonded to six oxygen atoms forming a distorted octahedral coordination sphere around the metal ion. Complexes 2 and 3 catalyse the ring opening metathesis reaction of norbornene when activated by Et₂AlCl.     

N-Hydroxyhomoazaadamantanone and its complexes with dioxo-molybdenum(VI) and copper(II): synthesis and structure

A hydroxamic acid of a new type, N-hydroxyhomoazaadamantanone (HL), has been synthesized, combining several structure peculiarities: cage skeleton, heterocyclicity, and rigidly fixed cis-orientation of the oxygens of the hydroxamate fragment of the molecule. Complexes of HL with dioxo-molybdenum(VI) ((MoO₂LC₂H₅OH)₂O) and copper(II) (CuL₂) have been synthesized. All compounds were characterized by IR and ¹H NMR spectroscopy. X-ray structural analyses of N-hydroxyhomoazaadamantanone hydrochloride and the coordination compounds have been carried out.     

A family of dioxo-molybdenum(VI) complexes of N2X heteroscorpionate ligands of relevance to molybdoenzymes

Four new Mo(VI)-dioxo complexes of a family of N2X heteroscorpionate ligands are reported which, together with data already available for (TpR)-, provide a unique example of a comprehensive set of isostructural, isoelectronic complexes differing only in one biologically relevant donor atom. A study of these complexes allows for a direct comparison of structural, spectroscopic, and oxygen atom transfer reactivity properties of the Mo(VI)-dioxo center (of relevance to various families of molybdoenzymes) as a function of donor atom identity.     

Synthesis and characterization of some novel ruthenium(II) complexes containing thiolate ligands

Reactions of the ruthenium complexes [RuH(CO)Cl(PPh₃)₃] and [RuCl₂(PPh₃)₃] with hetero-difunctional S,N-donor ligands 2-mercapto-5-methyl-1,3,5-thiadiazole (HL¹), 2-mercapto-4-methyl-5-thiazoleacetic acid (HL²), and 2-mercaptobenzothiazole (HL³) have been investigated. Neutral complexes [RuCl(CO)(PPh₃)₂(HL¹)] (1), [RuCl(CO)(PPh₃)₂(HL²)] (2), [RuCl(CO)(PPh₃)₂(HL³)] (3), [Ru(PPh₃)₂(HL¹)₂] (4), [RuCl(PPh₃)₃(HL²)] (5), and [RuCl(PPh₃)₃(HL³)] (6) imparting κ²-S,N-bonded ligands have been isolated from these reactions. Complexes 1 and 4 reacted with diphenyl-2-pyridylphosphine (PPh₂Py) to give neutral κ¹-P bonded complexes [RuCl(CO)(κ¹-P-PPh₂Py)₂(HL¹)] (7), and [Ru(κ¹-P-PPh₂Py)₂(HL¹)₂] (8). Complexes 1-8 have been characterized by analytical, spectral (IR, NMR, and electronic absorption) and electrochemical studies. Molecular structures of 1, 2, 4, and 7 have been determined crystallographically. Crystal structure determination revealed coordination of the mercapto-thiadiazole ligands (HL¹-HL³) to ruthenium as κ²-N,S-thiolates and presence of rare intermolecular S-S weak bonding interaction in complex 1.     

Synthesis and structure of lipophilic dioxo-molybdenum (VI) bis(hydroxamato) complexes

New methods for the synthesis of complexes of molybdenyl with hydrophobic alkyl-substituted hydroxamic acids have been developed. A number of novel coordination compounds of the general formula MoO₂L₂ (where HL is decano-, N-methyl-decano-, N-methyl-hexano-, N-methyl-1-adamantano- and N-tert-butyl-hexanohydroxamic acids) have been synthesized. All compounds obtained have been characterized by IR, ¹H NMR spectroscopy and X-ray crystallography. The effect of the electron donating and steric properties of ligand substituents on the structure of complexes is discussed.     

Mechanistic investigation of the oxygen-atom-transfer reactivity of dioxo-molybdenum(VI) complexes

The oxygen-atom-transfer (OAT) reactivity of [LiPrMoO2(OPh)] (1, LiPr=hydrotris(3-isopropylpyrazol-1-yl)borate) with the tertiary phosphines PEt3 and PPh2Me in acetonitrile was investigated. The first step, [LiPrMoO2(OPh)]+PR3-->[LiPrMoO(OPh)(OPR3)], follows a second-order rate law with an associative transition state (PEt3, DeltaH not equal=48.4 (+/-1.9) kJ mol-1, DeltaS not equal=-149.2 (+/-6.4) J mol-1 K-1, DeltaG not equal=92.9 kJ mol-1; PPh2Me, DeltaH not equal=73.4 (+/-3.7) kJ mol-1, DeltaS not equal=-71.9 (+/-2.3) J mol-1 K-1, DeltaG not equal=94.8 kJ mol-1). With PMe3 as a model substrate, the geometry and the free energy of the transition state (TS) for the formation of the phosphine oxide-coordinated intermediate were calculated. The latter, 95 kJ mol-1, is in good agreement with the experimental values. An unexpectedly large O-P-C angle calculated for the TS suggests that there is significant O-nucleophilic attack on the P--C sigma* in addition to the expected nucleophilic attack of the P on the Mo==O pi*. The second step of the reaction, that is, the exchange of the coordinated phosphine oxide with acetonitrile, [LiPrMoO(OPh)(OPR3)]+MeCN-->[LiPrMoO(OPh)(MeCN)]+OPR3, follows a first-order rate law in MeCN. A dissociative interchange (Id) mechanism, with activation parameters of DeltaH not equal=93.5 (+/-0.9) kJ mol-1, DeltaS not equal=18.2 (+/-3.3) J mol-1 K-1, DeltaG not equal=88.1 kJ mol-1 and DeltaH not equal=97.9 (+/-3.4) kJ mol-1, DeltaS not equal=47.3 (+/-11.8) J mol-1 K-1, DeltaG not equal=83.8 kJ mol-1, for [LiPrMoO(OPh)(OPEt3)] (2 a) and [LiPrMoO(OPh)(OPPh2Me)] (2 b), respectively, is consistent with the experimental data. Although gas-phase calculations indicate that the Mo--OPMe3 bond is stronger than the Mo--NCMe bond, solvation provides the driving force for the release of the phosphine oxide and formation of [LiPrMoO(OPh)(MeCN)] (3).     

cis‐Dioxomolybdenum(VI) complexes with unsymmetric linear tetradentate ligands: syntheses,structures and bromoperoxidase activities

Reactions of [MoO₂(acetylacetonate)₂], 2‐((2‐(2‐hydroxyethylamino)ethylamino)methyl)‐4‐R‐phenols (H₂Lⁿ, n = 1–5 for R = H, Me, OMe, Cl and Br, respectively) and KOH in 1:1:2 mole ratio in methanol afford a series of complexes having the general formula cis‐[MoO₂(Lⁿ)] ( 1 , 2 , 3 , 4 , 5 ) in 81–86% yields. The complexes have been characterized using elemental analysis, spectroscopy (infrared, UV–visible, and ¹H NMR, ¹³C NMR and ¹³C‐DEPT NMR) and electrochemical measurements. The molecular structures of 1 , 2 , 3 , 4 have been determined using single‐crystal X‐ray crystallography. In each of 1 , 2 , 3 , 4 , the ONNO‐donor 6,5,5‐membered fused chelate rings forming (Lⁿ)²⁻ and the two mutually cis oxo groups assemble a distorted octahedral N₂O₄ coordination sphere around the metal centre. In the crystal lattice, each of 1 , 2 , 3 , 4 forms a one‐dimensional infinite chain structure via intermolecular N  H⋅⋅⋅O hydrogen bonding interactions. In cyclic voltammograms, the diamagnetic complexes display an irreversible metal‐centred reduction in the potential range −0.73 to −0.88 V (vs Ag/AgCl). The physicochemical data are consistent with a very similar gross molecular structure for all of 1 , 2 , 3 , 4 , 5 . All the complexes exhibit decent bromoperoxidase activities and are also able to effectively catalyse benzoin and methyl(phenyl)sulfide oxidation reactions. Copyright © 2015 John Wiley & Sons, Ltd.     

Relation between intramolecular NH...S hydrogen bonds and coordination number in mercury(II) complexes with carbamoylbenzenethiol derivatives

A novel series of bis(carbamoylthiophenolato)mercury(II) complexes, [Hg(S-RNHCOC6H4)2] (1, R = 2-t-Bu; 2, R = 2-CH3; 3, R = 2-C6H5CH2; 4, R = 4-t-Bu), and a tetrakis(carbamoylthiophenolato)mercury(II) complex, (NEt4)2[Hg-(S-2-CH3NHCOC6H4)4] (5), were synthesized and characterized by 1H NMR, IR, 199Hg NMR, and crystallographic analyses. The bis(carbamoylthiophenolato)mercury complexes 1-3 do not have intramolecular NH...S hydrogen bonds between the amide NH group and the sulfur atom coordinated to mercury, whereas the tetrakis(thiophenolato)mercury complex 5 does have an intramolecular NH...S hydrogen bond. A relatively weak NH...S hydrogen bond in 5 can be seen in the 1H NMR spectra and the IR spectra in chloroform and in the solid state. The 199Hg NMR spectra in bis(carbamoylthiophenolato)mercury complexes 1-4 show a downfield shift, with an increase in the flow of electrons to mercury(II) from the oxygen atom due to the intramolecular Hg...O bonding interaction. Conversely, the 199Hg NMR spectra in 5 show a high-field shift with a decrease in the flow of electrons to mercury(II) from the sulfur atom due to the intramolecular NH...S hydrogen bond.     

Synthesis and structural characterization of a uranyl(VI) complex possessing unsupported unidentate thiolate ligands

The synthesis and structural characterization of the first example of a uranyl(VI) complex possessing unsupported unidentate thiolate ligands, UO2(S-2,6-Cl2C6H3)2L2 (2b, L=N,N-diisobutylisopropylamide), are reported. Isolation of 2b as a stable mononuclear complex is provided by the alkyl substituents of the organic amide ligands, which offer enhanced solubility, electron-releasing properties, and steric protection to help saturate the uranyl(VI) coordination sphere.     

Synthesis and characterization of peroxo complexes of uranium(VI) with aroylhydrazone ligands

The uranium(VI) peroxo complexes containing aroylhydrazones ligands having composition [UO(O₂)L-L(NO₃)₂]·H₂O (where L-L = Benzoic acid[1-(Furan-2-yl)methylene] hydrazide, Benzoic acid[(thiophene-2-yl)methylene] hydrazide, Benzoic acid[1-(thiophene-2-yl)ethylidene] hydrazide, Benzoic acid(phenylmethylene) hydrazide, Benzoic acid[1-(anisol-3-yl)methylene] hydrazide and Benzoic acid[(p-chlorobenzyl)methylene] hydrazide are reported. The complexes were characterized by various physico-chemical techniques, viz. elemental analysis, molar conductivity, magnetic susceptibility measurements, infra red, electronic, mass spectral and TGA/DTA studies. These studies revealed that complexes are non-electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode. Thermal analysis results provide conclusive evidence for the presence of water molecules in the complexes. Mass spectra confirm the molecular mass of the complexes. Antifungal activity of complexes revealed enhanced activity of complexes as compared to the corresponding ligands.     

Synthesis, characterization, and biomimetic chemistry of cis-oxosulfidomolybdenum(VI) complexes stabilized by an intramolecular Mo(O)=S...S interaction

The reactions of jade-green Tp*MoIVO(S2PR2) [Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; R = Et, Pri, Ph] with propylene sulfide produce ochre-red Tp*MoVIOS{SP(S)R2}. The complexes have been characterized by microanalysis, mass spectrometry, cyclic voltammetry, spectroscopy (IR, NMR, UV-vis, and X-ray absorption), and X-ray crystallography. The distorted-octahedral isopropyl and phenyl derivatives feature a tridentate fac-Tp* ligand, a terminal oxo ligand, and a unique five-membered Mo(=S){SP(=S)R2 ring moiety formed by a weak, intramolecular, bonding interaction between the Mo=S1 and (uncoordinated) S3=P moieties. The Mo=S1 [2.227(2) A (R = Pri) and 2.200(2) A (R = Ph)] and S1...S3 distances [2.396(3) A (R = Pri) and 2.383(2) A (R = Ph)] are indicative of a pi-bonded Mo=S1 unit and a weak (bond order ca. 1/3) S1...S3 interaction; the solid-state structures are maintained in solution according to S K-edge X-ray absorption data. The complexes react with excess cyanide to form thiocyanate and Tp*MoO(S2PR2), under anaerobic conditions, or Tp*MoO2(S2PR2), under aerobic conditions; the latter models the production of thiocyanate and desulfo molybdenum hydroxylases upon cyanolysis of molybdenum hydroxylases. The complexes react with triphenylphosphine to give Tp*MoO(S2PR2) and SPPh3, with cobaltocene or hydrosulfide ion to produce [Tp*MoVOS(S2PR2)]-, and with ferrocenium salts to yield [Tp*MoVO(S3PR2)]+; in the last two reactions, Mo(V) is produced by direct or induced internal redox reactions, respectively. The presence of the Mo(O)=S...S interaction does not radically lengthen the Mo=S bond in the complexes or preclude them from reactions typical of unperturbed oxosulfidomolybdenum(VI) complexes.     

Two dioxomolybdenum(VI) complexes with hydrazone ligands: synthesis,characterization, crystal structures and catalytic properties

A pair of Mo(VI) complexes, [MoO₂L¹(MeOH)] (1) and [MoO₂L²(MeOH)] (2), where L¹ and L² are the dianions of 2-amino-N’-(3-bromo-5-chloro-2-hydroxybenzylidene)benzohydrazide (H₂L¹) and 2-amino-N’-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (H₂L²), respectively, have been prepared and characterized by physico-chemical methods and single-crystal X-ray diffraction. The Mo atom in each complex is coordinated by the phenolate oxygen, imino nitrogen and enolate oxygen of the hydrazone ligand, together with a methanol ligand and two oxo groups, giving a distorted octahedral geometry. The complexes proved to be effective catalysts for the oxidation of various olefins.     

Syntheses, characterization, and photochromic studies of spirooxazine-containing 2,2'-bipyridine ligands and their zinc(II) thiolate complexes

A series of photochromic spirooxazine-containing zinc(II) diimine bis-thiolate complexes were successfully synthesized, and their photophysical and photochromic properties were studied. The X-ray crystal structure of complex 1a has also been determined. Upon excitation by UV light at 330 nm, all the ligands and complexes exhibit photochromic behavior. The thermal bleaching kinetics of the ligands and the complexes were studied in dimethylformamide at various temperatures. The photochemical quantum yields for the photochromic reactions of the ligands and complexes were also determined.     

Mono- and dinuclear Zn(II) complexes of Schiff-base ligands: syntheses,characterization and studies of photoluminescence

Six Schiff-bases HL¹-HL⁴, L⁵ and L⁶ [HL¹ = 2,6-bis[1-(2-aminoethyl)pyrolidine-iminomethyl]-4-methyl-phenol, HL² = 2,6-bis[1-(2-aminoethyl)piperidine-iminomethyl]-4-methyl-phenol, HL³ = N-{1-(2-aminoethyl)pyrolidine}salicylideneimine, HL⁴ = N-{1-(2-aminoethyl)piperidine}salicylideneimine, L⁵ = 2-benzoyl pyridine-N-{1-(2-aminoethyl)pyrolidine}, L⁶ = 2-benzoylpyridine-N-{1-(2-aminoethyl)piperidine}] have been synthesized and characterized. Zn(II) complexes of those ligands have been prepared by conventional sequential route as well as by template synthesis. The same complexes are obtained from the two routes as evident from routine physicochemical characterizations. All the Schiff-bases exhibit photoluminescence originating from intraligand (π–π*) transitions. Metal mediated fluorescence enhancement is observed on complexation of HL¹-HL⁴ with Zn(II), whereas metal mediated fluorescence quenching occurs in Zn(II) complexes of L⁵ and L⁶.     

Preparation and characterization of oxoperoxo tungsten(VI) complexes with morpholinomethyl urea and related ligands

The monooxodiperoxo complexes of tungsten(VI) of the type [WO(O₂)₂ L-L] (where L-L = morpholinomethyl urea, morpholinomethyl thiourea, piperidinomethyl urea, piperidinomethyl thiourea, pyrrolidinomethyl urea, and pyrrolidinomethy thiourea) have been synthesized and characterized by elemental analysis, IR, electronic spectra, magnetic susceptibility, and conductivity measurements, in addition to TGA/DTA. The energy-minimized structures of these complexes have been obtained by molecular modeling using Hyperchem release 7.52. The text was submitted by the authors in English.     

Intramolecular N-H...S hydrogen bonding in the zinc thiolate complex [Tm(Ph)]ZnSCH2C(O)NHPh: a mechanistic investigation of thiolate alkylation as probed by kinetics studies and by kinetic isotope effects

The zinc thiolate complex [Tm(Ph)]ZnSCH2C(O)N(H)Ph, which features a tetrahedral [ZnS4] motif analogous to that of the Ada DNA repair protein, may be obtained by the reaction of Zn(NO3)2 with [Tm(Ph)]Li and Li[SCH2C(O)N(H)Ph] ([Tm(Ph)] = tris(2-mercapto-1-phenylimidazolyl)hydroborato ligand). Structural characterization of [Tm(Ph)]ZnSCH2C(O)N(H)Ph by X-ray diffraction demonstrates that the molecule exhibits an intramolecular N-H...S hydrogen bond between the amide N-H group and thiolate sulfur atom, a structure that is reproduced by density functional theory (DFT) calculations. The thiolate ligand of [Tm(Ph)]ZnSCH2C(O)N(H)Ph is subject to alkylation, a reaction that is analogous to the function of the Ada DNA repair protein. Specifically, [Tm(Ph)]ZnSCH2C(O)N(H)Ph reacts with MeI to yield PhN(H)C(O)CH2SMe and [Tm(Ph)]ZnI, a reaction which is characterized by second-order kinetics that is consistent with either (i) an associative mechanism or (ii) a stepwise dissociative mechanism in which the alkylation step is rate determining. Although the kinetics studies are incapable of distinguishing between these possibilities, a small normal kinetic isotope effect of kH/kD = 1.16(1) at 0 degrees C for the reaction of [Tm(Ph)]ZnSCH2C(O)N(H*)Ph (H* = H, D) with MeI is suggestive of a dissociative mechanism on the basis of DFT calculations. In particular, DFT calculations demonstrate that a normal kinetic isotope effect requires thiolate dissociation because it results in the formation of [PhN(H)C(O)CH2S]- which, as an anion, exhibits a stronger N-H...S hydrogen bonding interaction than that in [Tm(Ph)]ZnSCH2C(O)N(H)Ph. Correspondingly, mechanisms that involve direct alkylation of coordinated thiolate are predicted to be characterized by kH/kD < or = 1 because the reaction involves a reduction of the negative charge on sulfur and hence a weakening of the N-H...S hydrogen bonding interaction.     

Synthesis and characterization of peroxo complexes of uranium(VI) with some Mannich base ligands

Abstract  

Uranium(VI) peroxo complexes of composition [UO(O₂)L–L(NO₃)₂], where L–L are the Mannich base ligands morpholinobenzyl urea, piperidinobenzyl urea, morpholinobenzyl thiourea, piperidinobenzyl thiourea, morpholinomethyl thiourea, piperidinomethyl thiourea, or morpholinomethyl urea, are reported. The synthesized complexes were characterized by use of a variety of physicochemical techniques, viz. elemental analysis, molar conductivity, magnetic susceptibility measurements, IR, electronic, mass, ¹H NMR, and ¹³C NMR spectroscopy, and TGA/DTA studies. These studies revealed that the complexes are both non-electrolytic and diamagnetic in nature. The ligands are bound to the metal in a bidentate mode through carbonyl oxygen or thiocarbonyl sulfur and the ring nitrogen. Mass spectra confirm the molecular mass of the complexes. The antifungal activity of the complexes is greater than that of the corresponding free ligands.     

Synthesis and characterization of oxodiperoxo complexes of tungsten(VI) with some Mannich base ligands

Six oxodiperoxotungsten(VI) complexes, [WO(O₂)₂L–L] (where L–L?=?morpholinobenzyl benzamide (MBB), piperidinobenzyl benzamide (PBB), piperidinobenzyl urea (PBU), morpholinobenzyl urea (MBU), piperidinobenzyl thiourea (PBTU) and morpholinobenzyl thiourea (MBTU)) have been prepared by stirring WO₃?·?H₂O with excess 30% aqueous (w/v) H₂O₂ and then treating with an ethanolic solution of the Mannich base ligand (L–L). These have been characterized by elemental analysis, conductance and magnetic susceptibility measurements, IR spectra, electronic spectra, ¹H NMR, TGA/DTA and cyclic voltammetric studies. These complexes are non-electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode through carbonyl oxygen/thiocarbonyl sulphur and the ring nitrogen. The complexes also inhibit the growth of pathogen “Fusarium Spp.” up to 60%. The cyclic voltammograms of the complexes indicate quasi-reversible redox steps involving complexes.