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1.
Consecutive synthesis methodologies for the preparation of a series of copper(I) formates [LmCuO2CH] (L = nBu3P: 4a, m = 1; 4b, m = 2; 5, L = [Ti](CCSiMe3)2, m = 1, [Ti] = (η5-C5H4SiMe3)2Ti) and [LmCuO2CH·HO2CR] (L = nBu3P: 7a, m = 1, R = H; 7b, m = 2, R = H; 7c, m = 2, R = Me; 7d, m = 2, R = CF3; 7e, m = 2, R = Ph. L = (cC6H11)3P, R = H: 8a, m = 2; 8b, m = 3. L = (CF3CH2O)3P, R = H: 9a, m = 2; 9b, m = 3. L = (CH3CH2O)3P, R = H: 10a, m = 2; 10b, m = 3. L = [Ti](CCSiMe3)2; m = 1: 11a, R = H; 11b, R = Ph) is reported using [CuO2CH] (1) and L (2a, L = nBu3P; 2b, L (cC6H11)3P; 2c, L = (CF3CH2O)3P; 2d, L = (CH3CH2O)3P; 3, L = [Ti](CCSiMe3)2) as key starting materials. Addition of formic acid (6a) or carboxylic acid HO2CR (6b, R = Me; 6c, R = CF3; 6d, R = Ph) to the afore itemized copper(I) formates 4 and 5 gave metal-organic or organometallic 7-11. The molecular structures of 8a and 11a in the solid state are reported showing a threefold coordinated copper(I) ion, setup by either two coordinatively-bonded phosphorus atoms and one formate oxygen atom (8a) or two π-bonded alkyne ligands and one oxygen atom (11a). A formic acid molecule is additionally hydrogen-bonded to the CuO2CH moiety. The use of 7b as suitable precursor for the deposition of copper onto TiN-coated oxidized silicon wafers by the spin-coating process below 300 °C is described. Complex 7b offers an appropriate transformation behavior into metal phase by an elimination-decarboxylation mechanism. The morphology of the copper films strongly depends on the annealing conditions. A closed grain network densified by a post-treatment is obtained (8 °C min−1, N2/H2 carrier gas). Hydrogen post-anneal to 420 °C after film deposition gave a copper film showing resistivities from 2.5 to 3.7 μΩ cm. This precursor was also used for gap-filling processes.  相似文献   

2.
Low pressure chemical vapour deposition (LPCVD) of [ZrCp2(NMe2)2] (1), [ZrCp22-MeNCH2CH2NMe)] (2), [ZrCp′2(NMe2)2] (3) and [ZrCp′2(NEt2)2] (4) (Cp = η5-cyclopentadienyl, Cp′ = η5-monomethylcyclopentadienyl), onto glass substrates at 600 °C, afforded highly reflective and adhesive films of zirconium carbide and amorphous carbon. Powder XRD indicated that the films were largely amorphous, although small, broad peaks accounting for ZrC and ZrO2 were present, suggesting that the remaining carbon was due to amorphous deposits from the cyclopentadienyl ligands. SEM images showed an island-growth mechanism with distinct crevices between the concentric nodules. Plasma-enhanced atomic layer deposition (PEALD) of compounds 1 and 2 showed that the precursors were not sufficiently stable or volatile to give a good rate of film growth.  相似文献   

3.
New silver (I) derivatives containing monodentate tertiary phosphanes and anionic poly(triazol-1-yl)borate ligands have been prepared from the reaction of AgNO3 and PR3 (R = Ph, Bn, o-tolyl, m-tolyl, p-tolyl) and potassium dihydrobis(1,2,4-triazolyl)borate, K[H2B(tz)2], or potassium hydrotris(1,2,4-triazolyl)borate, K[HB(tz)3]; their solid state and solution properties have been investigated through analytical and spectroscopic measurements (IR, 1H-, and 31P NMR). The 1H- and 31P NMR solution spectra in some cases can be interpreted on the basis of a dissociation of [{H2B(tz)2}Ag(PR3)2] into [{H2B(tz)2}Ag(PR3)] and PR3. All the compounds are soluble in chlorinated solvents and are non-electrolytes in CH2Cl2 and acetone solutions. [{H2B(tz)2}Ag(PPh3)2] and [{H2B(tz)2}Ag{P(m-tolyl)3}2] are simple mononuclear arrays, the silver atoms lying in four-coordinate N2AgP2 environments. Owing to the presence of the methyl substituents on the phosphane ligand, the complex [{HB(tz)3}Ag{P(o-tolyl)3}], as expected, is mononuclear. In [{H2B(tz)2}Ag{P(p-tolyl)3}], the silver environment is still four-coordinate but PAgN3, utilizing the coordinating capability of one of the additional (‘exo’-) ring nitrogens not only to complete the four-coordinate array about the silver but, necessarily, to link successive asymmetric units into a single-stranded polymer.  相似文献   

4.
From the interaction between azole-type ligands L and AgX (X = NO3 or ClO4) or [AgX(PPh3)n] (X = Cl, n = 3; X = MeSO3, n = 2), new ionic mononuclear [Ag(L)2]X and [Ag(PPh3)3L][X] or neutral mono-([Ag(PPh3)nL(X)]) or di-nuclear ([{Ag(PPh3)(L)(μ-X)}2]) complexes have been obtained which have been characterized through elemental analysis, conductivity measurements, IR, 1H NMR and, in some cases, also by 31P{1H} NMR spectroscopy, and single-crystal X-ray studies. Stoichiometries and molecular structures are dependent on the nature of the azole (steric hindrance and basicity), of the counter ion, and on the number of the P-donor ligands in the starting reactants. Solution data are consistent with partial dissociation of the complexes, occurring through breaking of both Ag-N and Ag-P bonds.  相似文献   

5.
Novel benzimidazolium salts were synthesized as N-heterocyclic carbene (NHC) precursors, these NHC precursors were metallated with Ag2O in dichloromethane at room temperature to give novel silver(I)–NHC complexes. Structures of these benzimidazolium salts and silver(I)–NHC complexes were characterized on the basis of elemental analysis, 1H NMR, 13C NMR, IR and LC–MS spectroscopic techniques. A series of benzimidazolium salts and silver(I)–NHC complexes were tested against standard bacterial strains: Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and the fungal strains: Candida albicans and Candida tropicalis. The results showed that benzimidazolium salts inhibited the growth of all bacteria and fungi strains and all silver(I)–NHC complexes performed good activities against different microorganisms.  相似文献   

6.
Treatment of MCl2(PP) or MCl2(PnPr3)2 with two equivalents of ArCOSeK readily yields cis-[M(SeCOAr)2(PP)] and trans-[M(SeCOAr)2(PnPr3)2], respectively (M = Pd or Pt; Ar = Ph or 4-MeC6H4; PP = dppm, dppe, dppp). The reaction of Pd(SeCOAr)2(dppe) with PdCl2(dppe) in the presence of NaBPh4 in methanol gave a tri-nuclear ionic complex, [Pd33-Se)2(dppe)3][BPh4]2. These complexes were characterized by UV-Vis, IR and NMR spectroscopy. The complex [Pt(SeCOPh)2(dppp)] has been structurally characterized by X-ray crystallography. The coordination environment around square planar platinum atom is defined by chelating dppp ligand and two unidentate selenocarboxylates bonded through selenium atoms. Pyrolysis of [Pd(SeCOAr)2(PnPr3)2] either in tri-n-butylphosphate (TBP) (at 200 °C) or in the solid state (furnace heating at 350 °C) gave Pd17Se15.  相似文献   

7.
The title compounds, for short Ag6(tsac)6 (1) and [Cu4(tsac)4(MeCN)2] · 2MeCN (2), were prepared by the reaction of thiosaccharin with Ag(I) or Cu(II) salts in different solvents. The new complexes were characterized by FT-IR, Raman, UV-Vis and NMR spectroscopy. Their crystal and molecular structures were determined by X-ray diffraction methods. The structures were solved from 1621 (1) and 7080 (2) reflections with I > 2σ(I) and refined to agreement R1-factors of 0.0261 (1) and 0.0456 (2). Ag6(tsac)6 molecule derives from the clustering of six Ag(tsac) moieties related to each other through the crystallographic 3-bar (S6) symmetry operations of the space group. This results in a highly regular molecular structure where the silver atoms are at the corners of an octahedral core slightly compressed along one of its three-fold axis [inter-metallic Ag?Ag contacts of 3.1723(4) and 3.1556(4) Å]. The six thiosaccharinate ligands bridge neighboring Ag atoms along the C3-axis through Ag-N bonds [d(Ag-N) = 2.285(2) Å] at one end and bifurcated Ag-S(thione)-Ag bonds [Ag-S distances of 2.4861(7) and 2.5014(8) Å] at the other end. In contrast, the 2 compound is arranged in the lattice as an irregular tetrameric copper complex [Cu4(tsac)4(MeCN)2] where the metals show different environments. Two copper ions are four-fold coordinated to three tsac ions through the N-atom of one tsac [Cu-N distances of 2.112(3) and 2.064(3) Å] and the thione sulfur atom of the other two [Cu-S distances in the range from 2.284(1) to 2.358(1) Å] and to a MeCN solvent molecule [Cu-N distances of 1.983(4) and 2.052(3) Å]. The other two copper ions are in three-fold environment, one trans-coordinated to two tsac ions [Cu-N distances of 1.912(3) and 1.920(3) Å] and to the thione S-atom of a third ligand [d(Cu-S) = 2.531(1) Å], the other one to the thione sulfur atom of three tsac ligands [Cu-S distances in the range from 2.229(1) to 2.334(1) Å]. The clustering renders the metals to short distances from each other, the shorter Cu?Cu distance being 2.6033(7) Å, as to presume the existence of weak inter-metallic interaction within the cluster.  相似文献   

8.
Reaction of phenylisothiocyanate with different aromatic amines allowed the synthesis of compounds containing the thiourea moiety. By reacting silver bis(triphenylphosphine)nitrate with suitable ligands belonging to this family of sulphurated compounds, three new complexes have been afforded. Ligands and complexes were characterized also by X-ray diffraction. The structures reveal remarkable differences in the silver coordination geometry in function of the nature and size of the ligand. The emission properties of all compounds were characterized at 10 and at 298 K.  相似文献   

9.
A series of new coumarin-derived carboxylate ligands and their silver(I) complexes have been synthesized, characterized and screened for their in vitro antibacterial activity against a range of Gram-positive and Gram-negative bacteria as well as for their antifungal activity against a clinical isolate of Candida albicans. The ligands were synthesised by either acid or base hydrolysis of their corresponding esters, which in turn were synthesised via the Knoevenegal reaction. The reaction of silver(I) nitrate with the coumarin carboxylate ligands in either aqueous or aqueous/ethanol solutions allowed the isolation of a series of novel Ag(I) carboxylate complexes. Whilst none of the ligands showed any antimicrobial activity, a number of the Ag(I) complexes exhibited potent activity. In particular, Ag(I) complexes of hydroxy-substituted coumarin carboxylates demonstrated potent activity against the clinically important methicillin-resistant Staphylococcus aureus (MRSA) bacterium (MIC80 = 0.63 μM).  相似文献   

10.
Adducts of triorganophosphines PR3, and diphosphines R2P(CH2)nPR2 with silver(I) diethyldithiocarbamate Ag(dtc) have been synthesized and characterized both in solution (1H, 31P NMR) and in the solid state (IR, single-crystal X-ray structure analysis). The topology of the structures in the solid state was found to depend on the nature of the P-donor and on the Ag(dtc):P-donor stoichiometric ratio. In the mononuclear [(Ph2MeP)2Ag(dtc)] and [{(:CHPPh2)2}Ag(dtc)], four-coordinate P2AgS2 environments are found, as also in [(dtc)Ag(P′-dppm-P′)2Ag(dtc)] where the two Ag(dtc) moieties are linked by the pair of bidentate, bridging, dppm ligands; by contrast the dppp adduct Ag(dtc):dppp (1:1) is an infinite one-dimensional polymer. In the other complexes [(R3P)Ag(dtc)]2 structurally defined, the silver environment is PAgS3, two of the sulfur atoms drawn from the same dtc, now an unsymmetrical chelate, and one of the sulfur atoms bridged to the second silver atom.  相似文献   

11.
Eight new coumarin substituted silver(I) N-heterocyclic carbene (NHC) complexes were synthesized by the interaction of the corresponding imidazolium or benzimidazolium chlorides and Ag2O in dichloromethane at room temperature. Structures of these complexes were established on the basis of elemental analysis, 1H NMR, 13C NMR, IR and mass spectroscopic techniques. The antimicrobial activities of carbene precursors and silver NHC complexes were tested against standard strains: Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and the fungi Candida albicans and Candida tropicalis. Results showed that all the compounds inhibited the growth of the all bacteria and fungi strains and some complexes performed good activities against different microorganisms. Among all the compounds, the most lipophilic complex bis[1-(4-methylene-6,8-dimethyl-2H-chromen-2-one)-3-(naphthalene-2-ylmethyl)benzimidazol-2-ylidene]silver(I) dichloro argentate (5e) was found out as the most active one.  相似文献   

12.
Several alkali metal hydroxoantimonates, K2[Sb(O)(OH)5], Na[Sb(OH)6], Cs[Sb(OH)6] and Cs2[Sb2(μ-O)2(OH)8] were isolated from aqueous solutions and characterized by single crystal and powder X-ray diffraction studies and by FTIR and thermal analysis. Crystal structures involving [Sb(O)(OH)5]2− were never anticipated before, and this is also the first disclosure of a dinuclear antimonate [Sb2(μ-O)2(OH)8]2−. Aqueous antimonate solutions of different pH were studied by high resolution electrospray mass spectrometry showing pH indifferent spectra and predominance of the mono and dinuclear antimonate species at pH 4-10.  相似文献   

13.
A series of NHC silver(I), mercury(II) and palladium(II) complexes, [(1,3-diethylbimy)6Ag4I3]I (2), [(1-benzyl-3-picolylbimy)Ag2Br2]n (3), [(1-benzyl-3-picolylbimy)HgI(CH2CN)]2 (4), {[(1-picolyl-3-npropylbimy)2Hg][Hg2I6]}n (5) and [(1,3-dipicolylbimy)PdCl]Cl (6), as well as one anionic complex [1,3-diethylbimidazolium]2[HgI4] (1) (bimy = benzimidazol-2-ylidene), have been prepared and characterized. Interestingly, a wind wheel-like Ag4I3 arrangement in 2 is formed, 1D polymeric chain containing 12-membered macrometallocycles and quadrangle Ag2Br2 units in 3 is generated, and the α-carbon atom of deprotonated acetonitrile ([CH2CN]) in 4 participates in coordination with mercury(II) atom. In the crystal packings of complexes 1-6, 2D supramolecular layers or 3D supramolecular architectures are formed via intermolecular weak interactions, including π-π interactions, hydrogen bonds, C-H···π contacts, weak Hg···I bonds and I···I bonds. Additionally, the catalytic activity of the NHC palladium(II) complex 6 in Suzuki-Miyaura cross-coupling reaction was studied.  相似文献   

14.
Two new complexes of platinum(II) and silver(I) with acesulfame were synthesized. Acesulfame is in the anionic form acesulfamate (ace). The structures of both complexes were determined by X-ray crystallography. For K2[PtCl2(ace)2] the platinum atom is coordinated to two Cl and two N-acesulfamate atoms forming a trans-square planar geometry. Each K+ ion interacts with two oxygen atoms of the S(O)2 group of each acesulfamate. For the polymeric complex [Ag(ace)]n the water molecule bridges between two crystallographic equivalent Ag1 atoms which are related each other by a twofold symmetry axis. Two Ag1 atoms, related to each other by a symmetry centre, make bond contact with two equivalent oxygen atoms. These bonds give rise to infinite chains along the unit cell diagonal in the ac plane. The in vitro cytotoxic analyses for the platinum complex using HeLa (human cervix cancer) cells show its low activity when compared to the vehicle-treated cells. The Ag(I) complex submitted to in vitro antimycobacterial tests, using the Microplate Alamar Blue (MABA) method, showed a good activity against Mycobacterium tuberculosis, responsible for tuberculosis, with a minimal inhibitory concentration (MIC) value of 11.6 μM. The Ag(I) complex also presented a promising activity against Gram negative (Escherichia coli and Pseudomonas aeruginosa) and Gram positive (Enterococcus faecalis) microorganisms. The complex K2[PtCl2(ace)2] was also evaluated for antiviral properties against dengue virus type 2 (New Guinea C strain) in Vero cells and showed a good inhibition of dengue virus type 2 (New Guinea C strain) replication at 200 μM, when compared to vehicle-treated cells.  相似文献   

15.
An overview of our work on the synthesis and biological activity of a series of tin(IV), silver(I) and antimony(III) complexes with thioamides is reported. Organotin(IV) complexes of formulae (n-Bu)2Sn(MBZT)2 (1), Me2Sn(CMBZT)(2) (2), {(Ph3Sn)2(MNA) (Me2CO)} (3), Ph3Sn(MBZT) (4), Ph3Sn(MBZO) (5), Ph3Sn(CMBZT) (6), Ph2Sn(CMBZT)2 (7) and (n-Bu)2Sn(CMBZT)2 (8), Me2Sn(PMT)2 (9), (n-Bu)2Sn(PMT)2 (10), Ph2Sn(PMT)2 (11), Ph3Sn(PMT) (12) {where MBZT=2-mercapto-benzothiazole, CMBZT=5-chloro-2-mercapto-benzothiazole, H2MNA=2-mercapto-nicotinic acid, MBZO=2-mercapto-benzoxazole and PMTH=2-mercapto-pyrimidine} were characterized by spectroscopic (NMR, IR, Mossbauer, etc.) and X-ray diffraction techniques and their influence on the peroxidation of oleic acid was studied. They were found to inhibit strongly the peroxidation of linoleic acid by the enzyme lipoxygenase. In addition, organotin(IV) complexes were found to exhibit stronger cytotoxic activity in vitro, against leiomyosarcoma cells, than cisplatin. The antiproliferative activity of the organotin complexes studied, against leiomyosarcoma cells follow the same order of LOX activity inhibition. This is, 3>12>7>6 approximately 8 approximately 10>5 approximately 4>2>9. Thus, among organotin(IV)-CMBZT complexes, 7 exhibits higher activity than the others and this is explained by a free radical mechanism, as it is revealed by an EPR study. The results are compared with the corresponding ones found for the silver(I) complexes of formulae complexes {[Ag6(mu3-HMNA)4(mu3-MNA)2](2-).[(Et(3)NH)+]2.(DMSO)2.(H2O)} (13), {[Ag4Cl4(mu3-STHPMH2)4]n} (14), {[Ag6(mu2-Br)6(mu2-STHPMH2)4(mu3-STHPMH2)2]n} (15), {[Ag4(mu2STHPMH2)6](NO3)4}(n) (16), {[AgCl(TPTP)]4} (17), [AgX(TPTP)3] with X=Cl (18), Br (19), I (20) (where STHPMH2=2-mercapto-3,4,5,6-tetrahydro-pyrimidine, TPTP=tri(p-toly)phosphine) and those of antimony(III) complexes {[SbCl2(MBZIM)4](+).Cl(-).2H2O.(CH3OH)} (21), {[SbCl2(MBZIM)4]+.Cl(-).3H2O.(CH3CN)} (22), [SbCl3(MBZIM)2] (23), [SbCl3(EMBZIM)2] (24), [SbCl3(MTZD)2] (25), {[SbCl3(THPMT)2]} (26) and {[Sb(PMT)3].0.5(CH3OH)} (27) (where MBZIM is 2-mercapto-benzimidazole, EMBZIM=5-ethoxy-2-mercapto-benzimidazole and MTZD is 2-mercapto-thiazolidine), which they have characterized with similar techniques as in case of organotin(IV) complexes. Silver(I) and antimony(III) complexes were found to be cytotoxic against various cancer cell lines.  相似文献   

16.
The reactions of a self-assembled silver(I) coordination polymer, [Ag2{μ-PriN(PPh2)2}(μ-NO3)2]n (1) with various bidentate N-donor ligands such as DABCO, 2,2′-bipyridyl and 1,10-phenanthroline yield 1-D helices or π-π stacked polymers, depending on the chelate vector of the N-donor ligand. The molecular structures of the resultant complexes, [Ag2{μ-PriN(PPh2)2}(DABCO)(NO3)2]n (2), [Ag2{μ-PriN(PPh2)2}(2,2′-bipy)2(NO3)2] (3) and [Ag2{μ-PriN(PPh2)2}(1,10-phen)2](NO3)2 (4) have been confirmed by single-crystal X-ray diffraction. Complex 2 exists as an infinite helical polymer because of the exo-bidentate nature of DABCO. Complex 3 assumes a 2D grid motif as a result of intermolecular π-π stacking among adjacent bipyridine moieties. The phenanthroline complex 4 exhibits strong inter- and intramolecular π-π stacking interactions.  相似文献   

17.
The bis(cyclopentadienyl) complexes [Cp2Ti(dca)]2O and Cp2V(dca)2 (dca = dicyanamide) have been prepared by reaction of sodium dicyanamide with aqueous solution of titanocene dichloride and vanadocene dichloride, respectively. The X-ray structure analyses of both complexes confirmed monodentate coordination of dicyanamide ligand through the terminal nitrogen atom of cyano group.  相似文献   

18.
Six new complexes, [Cu4I4(PPh2Cy)4]·2H2O (1), [CuI(PPhCy2)2] (2), [CuCl(PPhCy2)2] (3), and [CuBr(PPh3)3]·CH3CN (4), [Ag(PPhCy2)2(NO3)] (5), [Ag(PCy3)(NO3)]2 (6) [where Ph = phenyl, Cy = cyclohexyl], have been synthesized and structurally characterized by X-ray diffraction, IR absorption spectra and NMR spectroscopic studies (except complex 4). The X-ray diffraction analysis of complex (1), pseudo polymorph of complex [Cu4I4(PPh2Cy)4], reveals a stella quadrangula structure. The four corners of the cube are occupied by copper(I) atoms and four I atoms are present at the alternative corners of the cube, further more the copper(I) atoms are coordinated to a monodentate tertiary phosphine. Complexes (2) and (3) are isostructural with trigonal planar geometry around the copper(I) atom. The crystal structure of complex (4) is a pseudo polymorph of complex [CuBr(PPh3)3] and the geometrical environment around the copper(I) centre is distorted tetrahedral. In the AgI complexes (5) and (6), the central metal atoms have pseudo tetrahedral and trigonal planar geometry, respectively. Spectroscopic and microanalysis results are consistent with the single crystal X-ray diffraction studies.  相似文献   

19.
Six new adducts of the form AgX:PPh3:H2C(pzx)2 (1:1:1) (H2C(pzx)2 = H2C(pz)2 = bis(pyrazolyl)methane or H2C(pzMe2)2 = bis(3,5-dimethylpyrazolyl)methane; X = ClO4, NO3, SO3CF3) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, 1H and 31P NMR) and two of them also by single crystal X-ray diffraction studies for comparison with counterpart adducts with 2,2′-bipyridyl (‘bpy’) derivatives reported in a previous paper, the bpy-derived ligands forming five-membered chelate rings, while the present H2C(pzx)2 should, potentially, form six-membered rings. Such is the case, the two adducts exhibiting quasi-planar N2AgP coordination environments, perturbed by the approach of the oxyanion, unidentate in the case of the perchlorate but, in the case of the nitrate, an interesting disordered aggregate of differing unidentate modes.  相似文献   

20.
More than 130 delegates from all over the world attended the 1(st) Central and Eastern European Proteomic Conference organized together with the 3(rd) Czech Proteomic Conference in the TOP Hotel, Prague in the Czech Republic from 29(th) to 31(st) October, 2007. The autumn nostalgia of the historical city of Prague provided the stage for a fascinating meeting that reviewed rapidly emerging proteomic research in the countries of Central and Eastern Europe, and focused on proteomics driven discovery and applications.  相似文献   

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