Silver coordination and organometallic compounds: classification and analysis of crystallographic and structural data
TL;DR: In this article, a review summarizes the data for almost six hundred silver coordination and organometallic compounds, with the silver atom occurring in oxidation states of +1, +2, and two examples of +3 in a square-planar environment.
Abstract: This review summarizes the data for almost six hundred silver coordination and organometallic compounds, with the silver atom occurring in oxidation states of +1, +2, and two examples of +3 in a square-planar environment. The +2 oxidation state is found in digonal, square-planar, tetrahedral and hexa-coordinated environments. The +1 oxidation state is by far the most common in various geometries from two to seven. The nuclearity range from mono- to polynuclear utilizing a variety of ligand types. There are several examples of distortion isomerism, and a few examples of polymerization isomerism. Correlations between bond lengths, bond angles, ligating atom radius and silver oxidation state are discussed.
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TL;DR: In this paper, a review summarizes the most important aspect related to coordination chemistry of Ag(I) carboxylate complexes and their influence as antibacterial agents and concludes that the appearance of new bacterial strains resistant to antibiotics is a serious health problem; so, there is a strong incentive to develop new bactericides.
Abstract: Since ancient times, silver ions have been known to be effective against a broad range of micro-organisms but in the last decade, this metal has been greatly studied because of their antimicrobial capability against a wide range of bacteria, viruses, and fungi. For the same reason, it is the most extensively studied metal with antibacterial applications in medicine. Besides applications, the antimicrobial activity is associated with high effectiveness, low toxicity, and virtually no resistance of micro-organisms to the presence of this metal. The appearance of new bacterial strains resistant to antibiotics is a serious health problem; so, there is a strong incentive to develop new bactericides. This makes current research in bactericidal silver complexes particularly important. This review summarizes the most important aspect related to coordination chemistry of Ag(I) carboxylate complexes and their influence as antibacterial agents.
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TL;DR: In the presence of PPh3, a multidonor class of thiosemicarbazones has been shown to yield halogen-bridged dimers as mentioned in this paper.
Abstract: Reactions of thiosemicarbazones {R1R2C2═N3-N2(H)-C1(═S)-N1H2}, a multidonor class of ligands, with silver(I) halides in the presence of PPh3 have yielded a variety of compounds, viz.: (i) halogen-bridged dimers, [Ag2(μ-X)2(η1-S-Haptsc)2(PPh3)2] (R1 = Ph, R2 = Me, Haptsc, X = Cl (1); Br (2)), [Ag2(μ-Br)2(η1-S-Hbtsc)2(PPh3)2] (R1 = Ph, R2 = H, Hbtsc (3)), [Ag2(μ-Br)2(η1-S-Hactsc)2(PPh3)2] (R1 = R2 = Me, Hactsc (4)); (ii) sulfur-bridged dimers, [Ag2Br2(μ-S-Hptsc)2(PPh3)2]·2H2O (R1 = pyrrole, R2 = H, Hptsc (5)), and [Ag2Cl2(μ-S-Httsc)2(PPh3)2]·2CH3CN (R1 = thiophene, R2 = H, Httsc (6)), and (iii) monomers, [AgX(η1-S-Hpytsc)(PPh3)2]·CH3CN (R1 = pyridine, R2 = H, Hpytsc, X = Br (7); Cl (8)). In contrast, silver(I) nitrate has formed only sulfur-bridged dimers, [Ag2(η1-N-μ-S-Hftsc)2(Ph3P)2](NO3)2 (9) (R1 = furan, R2 = H, Hftsc), and [Ag2(η1-S-Hptsc)2(μ-S-Hptsc)2(Ph3P)2](NO3)2·2CHCl3 (10) (R1 = pyrrole, R2 = H, Hptsc) (Hpytsc = pyridine-2-carbaldehyde thiosemicarbazone, Hptsc = pyrrole-2-carbaldehyde thiosemicarb...
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TL;DR: Reactions of N-diphenylphosphanylmethylmethyl-4-aminopyridine (dppmapy) with K[Ag(CN)(2)], Ag(dca) (dca = dicyanamide), AgSCN, AgCl, AgBr or AgI gave rise to six [Ag(2)X(2)]-based compounds, which have photoluminescent properties of 1-6 in the solid state at ambient temperature
Abstract: Reactions of N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy) with K[Ag(CN)(2)], Ag(dca) (dca = dicyanamide), AgSCN, AgCl, AgBr or AgI gave rise to six [Ag(2)X(2)]-based (X = CN(-), dca, SCN(-), Cl(-), Br(-) and I(-)) compounds, [{Ag(2)(CN)(2)(dppmapy)}.0.5CHCl(3)](n) (1), [Ag(2)L(2)(dppmapy)(2)](n) (2: L = dca; 3: L = SCN), [{Ag(2)L(2)(dppmapy)(2)}.sol](n) (4: L = Cl, sol = 0.5MeOH.0.5CH(2)Cl(2); 5: L = Br, sol = 2CHCl(3)), and [Ag(2)I(2)(dppmapy)(4)].3MeOH (6). Complexes 1-6 were characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Compound 1 has a one-dimensional (1D) spiral chain constructed by bridging the [(CN)Ag(mu-CN)Ag] fragments via dppmapy ligands. In 2, 3 and 4, each [Ag(2)X(2)] (X = dca, SCN, Cl) fragment is linked by dppmapy bridges to the other two equivalent ones to form a 1D chain containing 16-membered rings (2) or a 1D double chain containing 20-membered rings (3) or a 1D spiral chain containing 20-membered rings (4). Compound 5 possesses a two dimensional (2D) (4,4) network consisting of 36-membered metallomacrocycles in which each [Ag(2)Br(2)] fragment acts as a unique planar four-connecting node to link the other four equivalent ones via dppmapy bridges. Complex 6 has a [Ag(2)I(2)] unit with a pair of monodentate dppmapy ligands coordinated at each Ag center. The photoluminescent properties of 1-6 in the solid state at ambient temperature were also investigated.
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TL;DR: In this article, the crystal structures of [Ag2(PPh3)4(EO4)]·2H2O (E ǫ = S 1 or Se 2) showed that these compounds contain three-coordinate silver and EO42− bridging the two silver atoms via two oxygen atoms, and a strong inverse correlation was found between 1J(107/109Ag,31P) and the Ag-P bond length.
Abstract: The crystal structures of [Ag2(PPh3)4(EO4)]·2H2O (E = S 1 or Se 2) showed that these contain [Ag2(PPh3)4(EO4)] units with three-coordinate silver and EO42− bridging the two silver atoms via two oxygen atoms. The complexes [Ag(PPh3)2(HEO4)]·H2O (E = S 3 or Se 4) contain [Ag(PPh3)2(HEO4)] molecules in which HEO4− is terminally bound to the silver atoms by a single oxygen atom. The complex [Ag(PPh3)2(H2PO4)]·2EtOH 5 contains [Ag(PPh3)2(H2PO4)] molecules in which H2PO4− is terminally bound to the silver atom, which is essentially three-coordinate. Heteronuclear 1J(107/109Ag,31P) and homonuclear 2J(31P,31P) spin–spin coupling constants for these compounds were determined by analysis of their high- (9.40 T) and very high-field (17.62 T) 31P CPMAS NMR spectra, with the aid of the 2-D 31P CPCOSY technique, and a strong inverse correlation was found between 1J(107/109Ag,31P) and the Ag–P bond length. IR and Raman studies show that the effect of a bound proton on the vibrational frequencies of EO42− is much greater than that of an attached metal atom.
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TL;DR: The crystal and molecular structures of four-coordinate silver and zinc tetraphenylporphyrinates have been determined in this article, and the average Ag-N distance is 2.092 A (individual values 2.045 (2) and 2.101 (3) A).
Abstract: The crystal and molecular structures of four-coordinate silver(I1) and zinc(I1) tetraphenylporphyrinates have been determined. Both complexes crystallize in the triclinic system and are isomorphous with the triclinic modification of the parent macrocycle H2TPP. Bond distances in the centrosymmetric coordination groups of both complexes are found to be statistically nonequivalent. Features of the crystal packing of the compounds suggest that this inequivalence arises from asymmetric lattice packing. The average Ag-N distance is 2.092 A (individual values 2.082 (3) and 2.101 (3) A), and that for Zn-N is 2.037 A (individual values 2.045 (2) and 2.029 (2) A). Crystal data for AgTPP: triclinic, a = 10.503 (2) A, b = 12.485 (2) A, c = 6.351 (2) A, a = 97.72 (l)', P = 100.68 (l)', y = 97.150 (9)', 2 = 1, space group Pi, 5616 observed data, R, = 0.059. Crystal data for ZnTPP: triclinic, a = 10.382 (1) A, b = 12.421 (2) A, c = 6.443 (1) A. 01 = 98.30 (I) ' , P = 101.15 (l)', y = 96.47 (I) ' , 2 = 1, space group Pi, 3729 observed data, R, = 0.036.
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