1192-40-1

The copper-catalyzed cyanation of disulfides by azobisisobutyronitrile (AIBN) was developed, leading to thiocyanates in moderate to good yields. This procedure tolerates a series of functional groups, such as chloro, nitro, methyl and methoxycarbonyl in the phenyl ring of disulfides. Notably, it enables the use of two ArS units in (ArS)2. CuI was found to be essential for the in situ formation of cyanide anions. This journal is

Organic bromides and iodides react with diorganodisulfides in the presence of stannous chloride and catalytic cupric halide, giving rise to corresponding unsymmetrical sulfides. Similar reactions but with elemental sulfur provide trisulfides and tetrasulf

A one-dimensional [Cu6I3(TP)3(MeCN)2]n (1) coordination polymer (CP) has been prepared by the direct reaction between CuI and a thiophenol (TP) ligand. The reversible conversion reaction between 1 and

Aerobic organisms must rely on abundant intracellular thiols to reductively protect various vital functional units, especially ubiquitous zinc(II) thiolate sites of proteins, from deleterious oxidations resulting from oxidizing environments. Disclosed here is the first well-defined model study for reactions between zinc(II) thiolate complexes and copper(II) complexes. Among all the studied ligands of copper(II), diethyldithiocarbamate (DTC) displays a unique redox-tuning ability that enables copper(II) to resist the reduction by thiols while retaining its ability to oxidize zinc(II) thiolates to form disulfides. This work proves for the first time that it is possible to develop oxidants to discriminate between thiols and zinc(II) thiolates, alluding to a new chemical principle for how oxidants, especially universal anticancer Cu(DTC)2, might circumvent the intracellular reductive defense around certain zinc(II) thiolate sites of proteins to kill malignant cells.

Copper chalcogenide nanoparticles (Cu2S) synthesized for the first time from a single-source precursor, CuSPh, act as highly efficient and reusable heterogeneous catalyst for regioselective amination of N,N-dimethylbenzylamines with various azo

CuI N-heterocycle thiolate clusters efficiently catalyze the acceptorless dehydrogenation of alcohols at 70 °C. A variety of secondary/primary benzylic, allylic, and aliphatic alcohols are dehydrogenated to the corresponding ketones and aldehydes in high yields of isolated product upon release of H2. This simple catalytic system is involved in the synthesis of imines through the one-pot reaction of alcohols and amines.

Highly active and selective aerobic cross-dehydrogenative coupling of terminal alkynes with thiols to construct alkynyl sulfides catalyzed by Cu(i) using molecular oxygen as the oxidant has been demonstrated under mild reaction conditions. The process is applicable to a wide range of alkynes and various thiols and is compatible with a variety of functional groups on both alkyne and thiol coupling partners.

Copper (I) salts of various anions including thiolates, diethyl dithiocarbamate, diethyl dithiophosphate, trithiocyanurate, 1-cyano-3- methylisothiourea, 2-aminothiazole, and tetrakis(1-imidazolyl)borate are conveniently synthesized by reducing copper (II) sulfate in aqueous ammonia. The addition of phosphine ligands to several of the products is demonstrated, and the crystal structure of [Cu2(MBT)2(DPPE)3] ? Et2O (MBT = 2-mercaptobenzothiazolate, DPPE = 1,2-bis(diphenylphosphino)ethane) is reported.

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Compounds of formula (I) are disclosed: STR1 wherein L1 is a main group atom, L2 is a neutral ligand, M is a transition element or a metal element of Group 13, 14, 15, or 16 of the Periodic Table, x is the number of coordination sites of M, R1 is a polymerizable group, R2, R3, and R4 are ligands, and R5 is an anionic ligand. The compounds or monomers of formula (I) are capable of conversion to polymers by combination with one or more other known monomers, such as methyl methacrylate. Such polymers can then be added as a binder in a paint formulation to make marine antifouling coating compositions. Also described is a method to prevent fouling on surfaces wherein a composition containing a metal complex compound of formula (II): STR2 wherein M, x, L2, n, and R4 have the same meaning as in formula (I), is applied to the surface susceptible to fouling.

The synthesis and characterization of the complexes [(η5-C5H4SiMe3) 2Ti(C≡CSiMe3)2]MX (M = Cu, X = OTf (2), SC6H5 (4), SC6H4NMe2-2 (5), SC6H4CH2NMe2-2 (6), S-1-C10H6NMe2-8 (7), Cl (8), (N≡CMe)PF6 (9); M = Ag, X = OTf (3)) are described. These complexes contain monomeric MX entities, which are η2-bonded by both alkyne functionalities of the organometallic bis(alkyne) ligand [(η5-C5H4SiMe3) 2Ti(C≡CSiMe3)2] (1). The reactions of 2 with the Lewis bases N≡CPh and N≡CC (H)=C (H)C≡N afford the cationic complexes {[(η5-C5H4SiMe3) 2Ti(C≡CSiMe3)2]Cu(N≡CPh)}OTf (10) and {[η5-C5H4SiMe3) 2Ti(C≡CSiMe3)2]Cu}2(N≡CC (H)=C (H)C≡N)(OTf)2 (11), respectively. The X-ray structures of 2, 3, and 6 have been determined. Crystals of 2 are monoclinic, space group P21/c, with a = 12.8547(7) A, b = 21.340(2) A, c = 18.279(1) A, β= 133.623(5)°, V = 3629.7(5) A3, Z = 4, and final R = 0.047 for 5531 reflections with I > 2.5σ (I) and 400 variables. The silver triflate complex 3 is isostructural, but not isomorphous, with the corresponding copper complex 2, and crystals of 3 are monoclinic, space group P21/c, with a = 13.384(3) A, b = 24.55(1) A, c = 13.506(3) A,β = 119.21(2)°, V = 3873(2) A3, Z = 4, and final R = 0.038 for 3578 reflections with F ≥ 4σ (F) and 403 variables. Crystals of the copper arenethiolate complex 6 are triclinic, space group P1 with a = 11.277(3) A, b = 12.991(6) A, c = 15.390(6) A, α = 65.17(4)°, β= 78.91(3)°, γ = 84.78(3)°, V = 2008(2) A3, Z = 2, and final R = 0.079 for 6022 reflections and 388 variables. Complexes 2-11 all contain a monomeric bis(η2-alkyne)M(η1-X) unit (M = Cu, Ag) in which the group 11 metal atom is trigonally coordinated by the chelating bis(η2-alkyne) entity Ti(C≡CSiMe3)2 and an η1-bonded monoanionic ligand X. The copper arenethiolate complexes 4-7 are fluxional in solution.

Raman spectra of noble-metal phenylthiolates and the corresponding surface-enhanced Raman (SER) spectra of the surface species on copper, silver, and gold are reported.Periodic trends were found in both the bulk Raman spectra of the phenylthiolates and the SER spectra.Intensities of the Raman spectra approach that of liquid thiophenol as the metal changes from copper to silver to gold.The SER spectra were used to obtain orientations of the thiophenol species at the noble-metal surfaces.Orientations were determined through the electric field enhancement of vibrations normal to the metal surface.The model developed in this paper allows one to determine both the azimuthal and axial angles of C2ν molecules at surfaces.This is possible by performing the SERS measurement in media of differing indexes of refraction.For silver and gold we found the axial angle Θ = 85 and 76 deg, respectively.The azimuthal angle Φ was found to vary from 32 to 0 deg from silver to gold.The SER spectra of copper were too weak for accurate angle determinations with a surrounding media other than air.However, the SER spectrum observed on copper in air does indicate a near-perpendicular orientation.

The electrochemical oxidation of anodic copper or silver (= M) into non-aqueous solutions of RSH (R = alkyl, axyl) gives MISR as insoluble materials in high yield.In the presence of 1,10-phenanthroline (= L), the products are MISR*phen for M = Cu, but not Ag.Gold resists oxidation under such conditions, and AuISR (R = n-C4H9, C6H5) was obtained in only poor yield.The crystal structure of the solvated dimeric adduct 2*CH3CN is triclinic, with a = 10.682(3) Angstroem, b = 11.729(4) Angstroem, c = 15.608(5) Angstroem, α = 76.87(2) deg, β = 76.35(2) deg, γ = 68.07(2) deg, V = 1742(1) Angstroem3, Z = 2 and space group P1.The structure is based on a folded Cu2S2 ring with an unusually short Cu-Cu distance of 2.613(3) Angstroem.Each copper atom has CuS2N2 pseudo-tetrahedral stereochemistry, with Cu-S = 2.337 Angstroem (av) and Cu-N = 2.10 Angstroem (av).

The electrochemical oxidation of anodic copper in an acetonitrile solution of RSH (R = Ph, C10H7, CPh3, C6F4H, o-MeC6H4, CMe2Et) yields CuSR; treatment of CuSCMe2Et with CS2 produces Cu8(SR)4(S2CSR)4, whose structure is based on an unusual Cu8S12 cage.

The reaction of thiophenol (PhSH) with metallic copper affords CuSPh and H2 through Cu-catalyzed dehydrogenative coupling of PhSH to PhSSPh and ensuing addition of PhSSPh to Cu.Condensation between thiophenols (ArSH) and aryl iodides or bromides (Ar'X) in the presence of Cu affords diaryl sulfides (ArSAr') in good or moderate yields (ArSH + Ar'X + Cu -> ArSAr' + CuX + 1/2 H2).Use of alkyl iodides (RI), instead of Ar'X, affords alkyl aryl sulfides (ArSR) in good yields.These condensations are considered to proceed mainly through (1) copper-catalyzed dehydrogenative coupling of ArSH to ArSSAr with evolution of H2, (2) addition of ArSSAr to Cu giving CuSAr, and (3) coupling of CuSAr with Ar'X giving ArSAr'and CuX; temperature dependence of products, time course of the reaction, the reaction of PhSSPh with Cu, and the reaction of Ar'X with CuSPh support this view.Use of copper oxides (Cu2O and CuO), instead of Cu, also affords diaryl sulfides in good or moderate yields.

The preparation and the crystal structure of a copper(I) complex with the deprotoned S-Butyldithiocarbanilic ester is described.The crystals of Cu are rhombohedral with one hexameric unit in the unit cell.

Pale yellow (Ph3P)2Cu(μ-SPh)2Cu(PPh3) 2 has been crystallized from a mixture of CuSPh and Ph3P in chloroform/propanol. The pseudotetrahedra around the equivalent copper atoms are linked at the common edge formed by the bridging thiolate ligands, such that the four phosphorus atoms and the two copper atoms are virtually coplanar. The molecule contains a crystallographic twofold axis that passes through both benzenethiolate ligands, and accordingly, the stereochemistry at sulfur is strictly planar. This is the first reported instance of planar stereochemistry at sulfur in a thiolate ligand bridging two metal atoms. There is crowded packing of the phenyl rings of the four Ph3P ligands around the equatorial girdle of the molecule, an effect that restricts any movement of the axial SPh ligands away from planarity at sulfur and also increases the separation between the two copper atoms. Key dimensions: Cu-S, 2.344 (4), 2.415 (4) A?; Cu-P, 2.304 (2), 2.308 (2) A?; S-Cu-S, 79.3 (2)°; P-Cu-P, 118.3 (1)°; Cu-Cu, 3.662 (2) A?. Crystal data: prisms, C87H70Cu2P4S2, mol wt 1394.6, tetragonal, a = 14.071 (1) A?, c = 17.720 (2) A?, P42/m (disordered structure), Z = 2, Mo Kα radiation, 1775 observed data, R = 0.064, Rw = 0.077.

Electrical conductivities of copper(I) mercaptide complexes of aromatic and heteroaromatic mercaptans have been measured and a conduction mechanism is discussed.The observed conductivities are highly substitution-dependent and vary in the range of 1E-4 to 1E-10 ohm-1 cm-1 at 25 deg C.The solid state absorption spectra and the pressure-induced colour change of the complexes indicate creation of mixed-valence Cu(I)-Cu(II) species which appear to be responsible for their relatively high conductivities.A model which assumes electron hopping assisted by Cu-S stretching frequency along the -Cu-S-Cu-S- conducting spine formed in the S-bridged polymeric structures of these complexes is suggested for the conduction process.