Synthesis and structural characterization of the adducts of silver(I) perchlorate and nitrate with triphenylphosphine and bis(pyrazolyl)methane ligands of 1:1:1 stoichiometry

Six new adducts of the form AgX:PPh₃:H₂C(pz^x)₂ (1:1:1) (H₂C(pz^x)₂ = H₂C(pz)₂ = bis(pyrazolyl)methane or H₂C(pz^Me2)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(pz^x)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.     

Silver(I) complexes with heterocyclic thiones and tertiary phosphines as ligands. Part 4. Dinuclear complexes of silver(I) bromide: the crystal structure of bis[bromo-(pyrimidine-2-thione)(triphenylphosphine)silver(I)]

Mixed-ligand complexes of the formula [Ag(PPh₃)(L)Br]₂ were obtained by treatment of various heterocyclic thiones L {L=pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH), benz-1,3-imidazoline-2-thione (bzimtH₂), benz-1,3-thiazoline-2-thione (bztztH), 1-methyl-1,3-imidazoline-2-thione (meimtH) and 5-methoxy-benz-1,3-imidazoline-2-thione (5MeObzimtH₂)} with equivalent quantities of silver(I) bromide and triphenylphosphine in dry acetone. The compounds were characterized by their IR, far-IR, UV–Vis and ¹H NMR spectroscopic data. The crystal structure of [Ag(PPh₃)(pymtH)Br]₂ was determined by single-crystal X-ray diffraction methods. The complex exhibits a planar Ag₂Br₂ moiety in which each of the doubly bromine-bridged Ag(I) centres is further bonded to one phosphine P and one thione S atom.     

Syntheses and characterizations of six hydrogen-bonded silver(I) complexes from assembly of silver(I) nitrate and aminobenzoic acid

Six hydrogen-bonded silver(I) complexes, Ag(4-abaH)₂(NO₃) (1), [Ag(4-abaH)₂(NO₃)]_n (2), {[Ag(4-aba)(4-abaH)] · H₂O}_n (3), {[Ag(4,4^′-bipy)(H₂O)](4-aba)_0.5(NO₃)_0.5 · (H₂O)_0.5}_n (4), [Ag[(3-abaH_0.5)₂] (5), and {[Ag(3-aba)] · H₂O}_n (6) (4-abaH=4-aminobenzoic acid, 3-abaH=3-aminobenzoic acid), have been synthesized and characterized by single-crystal X-ray diffraction analyses. In 1, 4-abaH serves as a monodentate ligand coordinating to Ag(I) through its nitrogen atom, while uncoordinated carboxylic group links (4-abaH)-Ag-(4-abaH) into a one-dimensional metallic carboxylic synthon. 2 may be regarded as an extension of 1 into a two-dimensional carboxylic synthon through NO₃ ⁻ bridging two adjacent Ag(I) centers. In 3, 4-abaH in a monodentate mode and 4-aba in a μ-N,O bridging mode link three-coordinated Ag(I) to form a one-dimensional swallow-like chain, which is further extended into a two-dimensional layer structure through inter-chain hydrogen bonding interactions. The alternating Ag(I) and 4,4^′-bipy in 4 give rise to a slightly distorted linear chain, which is further extended into a two-dimensional layer through the completely overlapping and off-set stacking interactions. The hydrogen bonds involving in weakly coordinated aqueous molecules and 4-aba further extend it into a three-dimensional framework. In 5, the inter-molecular hydrogen bonding and π-π stacking interactions extend Ag[(3-abaH_0.5)₂] into a two-dimensional supramolecular architecture. In 6, 3-aba in a μ₃-N,O,O^′ coordination mode links three three-coordinated Ag(I) into a two-dimensional network. Uncoordinated aqueous molecules and the adjacent 3-aba oxygen atoms form intermolecular hydrogen bonds.     

Syntheses, structures and vibrational spectroscopy of some 1:2 and 1:3 adducts of silver(I) oxyanion salts with pyridine and piperidine bases containing non-coordinating 2(,6)-substituents

Synthetic, single crystal X-ray structural characterizations and vibrational spectroscopic studies are recorded for a number of adducts of 1:2 stoichiometry of silver(I) oxyanion salts for oxyanions of differing basicity (perchlorate, nitrate, carboxylate (as trifluoroacetate (≡‘tfa’))), with a variety of pyridine (≡‘py’) or piperidine (≡‘pip’) bases hindered in the 2- (and, sometimes, 6-) position(s) by methyl or non-coordinating functionalities of other types, the ligands employed being 2-methylpyridine (‘2mp’), 2,6-dimethylpyridine (‘lut’), 2,4,6-trimethylpyridine (‘coll’), quinoline (‘quin’), 2,2,6,6-tetramethylpiperidine (‘tmp’), 2-amino-,6-methylpyridine (‘nmp’), 2-methoxypyridine (‘mop’) and 2-cyanomethylpyridine (‘pcn’); studies are also recorded of adducts with the parent, ‘py’, base and with 4-cyanopyridine (‘cnp’). In the majority of the complexes, the NAgN motif predominates, as might be expected, variously distorted from linearity in response to changes in (competing) basicities of the nitrogen base and any nearby anion or solvent molecule; an unusual variation is found in the highly hindered tmp/tfa adduct which is a monohydrate with interacting water displacing the rather basic anion, the converse being the case in the corresponding nitrate, also a monohydrate. With the less-hindered base mpy, both nitrate and trifluoroacetate are binuclear, with O and OCO bridges corresponding to centrosymmetric four- and eight-membered rings, respectively; the quin/nitrate adduct is more complex, also binuclear but with bis(chelating) nitrate. AgNO₃:py (1:3) is found to be binuclear, while with Agtfa/py, a 3:2 adduct [Ag(py)₂][Ag₂(tfa)₃]_(∞|∞) is found with a novel, polymeric, strongly interacting anion. A further pair of 1:3 adducts, AgNO₃:2np (2np = 2-aminopyridine) and Agtfa:nmp, both mononuclear [AgL₃]⁺X⁻ are described, differing in the modes of interaction of silver with the three N-bases. In all simple NAgN systems with aromatic ligands, the pair of ligand ‘planes’ is disposed quasi-parallel.The far-IR spectra of [AgL₂]Y (L = lut, coll; Y = ClO₄, NO₃, tfa) and of [Ag(py)_n](ClO₄) (n = 2,4) have been recorded and the ν(AgN) bands assigned in the range 80-240 cm⁻¹. For the L = lut, coll complexes, there is a clear trend of decreasing ν(AgN) following increasing r(AgN) as the interaction with the counterion increases along the series Y = ClO₄, NO₃, tfa.     

Syntheses and structures of some adducts of silver(I) oxyanion salts with some 2-N,O-donor-substituted pyridine bases

Syntheses and room-temperature single crystal X-ray structural characterizations are recorded for a variety of silver(I) oxyanion (perchlorate, nitrate and trifluoroacetate (‘tfa’) (increasing basicity)) adducts, AgX, with a number of pyridine (‘py’) bases, L, functionalized in the 2-position with N- or O-donor groups, namely 2-amino-, 2-amino-6-methyl-, 2-aminomethyl-, 2-hydroxy-, 2-methoxy- and 2-acetyl- pyridines, ‘2np’, ‘nmp’, ‘amp’, ‘ohp’, ‘mop’, and ‘acp’. A variety of stoichiometries and associated structural types are defined: [Ag(chelate)₂]X, L/X = amp,acp/ClO₄, [XAg(chelate)₂], L/X = acp/tfa, of 1:2 AgX:L stoichiometry; for 1:1 stoichiometry, although a discrete mononuclear complex [(chelate)Ag(O₂NO)] is defined for AgNO₃: acp (1:1), all others are polymers, successive silver atoms being linked by N,N′-bridging ligands singly (L/X = 2np/ClO₄ (?HAgHTAgTHAgH?), amp/ClO₄, NO₃ (?HTAgHTAg?) (‘H’ ≡ head, ‘T’ = tail)) or pairwise, ?L₂AgX₂AgL₂Ag? (L/X = 2np/tfa, nmp/NO₃). More complex polymeric arrays are found with L/X = ohp/NO₃, tfa, where interaction with the metal takes place via the O-donor only, the py functionality being protonated, and in adducts of more complex stoichiometry AgNO₃:mop (2:3) and AgNO₃:2np (3:4).     

Synthesis and structural characterization of mixed-ligand silver(I) complexes containing diphosphazanes and bidentate N-donor ligands

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.     

Complexation of silver(I) cation by a series of heterosubstituted dipyridyl ligands

The synthesis of a series of dipyridyl ligands based on 1,2-bis(2′-pyridylethynyl)benzene and their complexation of silver cation is described. NMR binding studies confirm that the incorporation of thioether appendages results in an increased binding constant while ether appendages result in similar or lower binding constants as compared to the unsubstituted ligand. X-ray crystallographic analysis confirms that steric hinderance is critical.     

Synthesis and structural studies of dimolybdenum(V), palladium(II) and dicopper(I) complexes that contain mixed pyridyl-iso-propylphosphine ligands

The reaction of Mo₂(μ-O₂CCH₃)₄ with 2-pyridyl(diisopropylphosphino)methane (NP) affords the dimolybdenum(V) complex Mo₂(μ-O)₂O₂Cl₂(η²-NP)₂ (1). Complexes of the related 2-pyridylbis(diisopropylphosphino)methane ligand (NP²) have been isolated, namely, a mixed bromo/chloro complex of composition PdBr_1.09Cl_0.91(η²-NP²) (2) and the dicopper(I) complex [Cu₂(μ-η³-NP²)₂](BF₄)₂ (3). The structures of 1, 2 and 3 have been established by X-ray crystallography.     

Silver derivatives of tris(pyrazol-1-yl)methanes. A silver(I) nitrate complex containing a tris(pyrazolyl)methane coordinated in a bridging mode

The reaction of AgX (X=ClO₄, NO₃ or SO₃CH₃) acceptors with excesses of tris(pyrazol-1-yl)methane ligands L (L=CH(pz)₃, CH(4-Mepz)₃, CH(3,5-Me₂pz)₃, CH(3,4,5-Me₃pz)₃ or CH(3-Mepz)₂(5-Mepz)) yields 1:1 [AgX(L)], 2:1 [Ag(L)₂]X or 3:2 [(AgX)₂(L)₃] complexes. The ligand to metal ratio in all complexes is dependent on the number and disposition of the Me substituents on the azole ring of the neutral ligand and on the nature of the Ag(I) acceptor. All complexes have been characterized in the solid state as well as in solution (medium- and far-IR, ¹H and ¹³C NMR and conductivity determinations) and the solid-state structures of [Ag(NO₃){(pz)₃CH}]_(∞/∞) and [Ag{(3,5-Me₂pz)₃CH}₂]NO₃ determined by single crystal X-ray studies.     

Gold(I) and silver(I) complexes of 2,3-bis(diphenylphosphino)maleic acid: Structural studies and antitumour activity

The 2:1 and 1:2 adducts of Au(I) and 1:2 adducts of Ag(I) with the diphosphine 2,3-bis(diphenylphosphino)maleic acid (dpmaa) have been prepared in high yields. Crystal structures have been determined for the neutral digold complex (AuCl)₂(dpmaa) · 2thf (1) and the bis-chelated complex [Au(dpmaa)₂]Cl · H₂O · CH₃OH (2). For 1, conformational rigidity imposed by the ethylenic bridge facilitates the formation of short intramolecular Au-Au contacts with no evidence of similar intermolecular contacts. Complex 2 crystallizes with [Au(dpmaa)₂]⁺ cations hydrogen bonded through the carboxyl groups to a water molecule and chloride anion to form a H-bonded chain along the a axis. ³¹P NMR titration of 1 with dpmaa in acetone shows conversion to 2 at Au:P-P ratios less than 1:1 indicating similar high thermodynamic and kinetic stabilities to other bis-chelated [Au(P-P)₂]⁺ complexes containing 5- or 6-membered chelate rings. The ionic Au(I) complex 2 and the analogous Ag(I) complex [Ag(dpmma)₂]NO₃ (3) are highly water soluble. The in vitro cytotoxic activity of 2 was assessed against eight different cell lines and no significant activity was found. The solubility properties and solution behaviour of the complexes are compared to the analogous 1,2-bis(diphenylphosphino)ethane (dppe) complexes and the potential significance of these results to the antitumour properties of chelated 1:2 Au(I)diphosphine complexes are discussed.     

Synthesis, crystal structures and in vitro anti-fungal activities of two silver(I) coordination polymers with fluconazole

Two new polymeric silver(I)-fluconazole complexes: [Ag(HFlu)(NO₃)]_n (1) and {[Ag(HFlu)₂](ClO₄)}_n (2), have been synthesized and structurally characterized. The crystal structure of 1 consists of infinite 1D single strand helical coordination arrays with alternative …PMPM… arrangements, which are interlinked through hydrogen bonding interactions to generate a 3D network. The shortest intrachain Ag?Ag distance bridged by HFlu ligand is 8.287(1) Å. In 2, each Ag(I) ion is coordinated by four triazole N atoms from four HFlu ligands to form a 2D coordination layer, which has a helical arrangement along the [1 0 0] direction. The results of anti-fungal studies demonstrate that both silver(I) complexes are more active in comparison to the fluconazole drug.     

Palladium complexes with PCP ligands.: Preparation and structural studies of two forms of [(PCP)Pd(OH2)]BF4

Abstraction of chloride from the Pd complex {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]PdCl with AgBF₄ in THF gives {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(THF)}⁺BF₄ ⁻. Attemped crystallization of this THF complex produced the aqua complex {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(OH₂)}⁺BF₄ ⁻. Crystal structures of two crystalline forms of this compound are reported. In {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(OH₂)}⁺BF₄ ⁻·THF, one hydrogen of the water is hydrogen bonded to the oxygen of the THF, and the other hydrogen is hydrogen bonded to an F of the BF₄ ⁻ anion. Another crystalline form has no THF, but has both of the hydrogens of water hydrogen bonded to different BF₄ ⁻ anions, such that two different BF₄ ⁻ anions bridge two {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(OH₂)}⁺ cations. A crystal structure is also reported for the palladium chloride complex [η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]PdCl.     

Silver(I) methanesulfonate complexes containing diphosphine ligands: Spectroscopic and structural characterization

1:1 and 2:1 adducts of diphosphine ligands R₂P(R′)_nPR₂ (dppm: R = Ph, R′ = CH₂, n = 1; dppe: R = Ph, R′ = CH₂, n = 2; dppp: R = Ph, R′ = CH₂, n = 3; dppb: R = Ph, R′ = CH₂, n = 4; dppf: R = Ph, R′ = ferrocenyl, n = 1) with silver(I) methanesulfonate have been synthesized and characterized both in solution (¹H, ³¹P NMR) and in the solid state (IR, single crystal X-ray structure analysis). The two different stoichiometries have been found to depend on the molar ratio of ligand to metal employed and the nature of the diphosphine ligand. In AgO₃SMe:dppp,dppb (1:1)₂, in the [Ag(P^P)₂Ag] arrays, the silver atoms are also bridged by anion oxygen atoms, in disparate fashion commensurate with the different Ag?Ag distances.     

Solid state and solution NMR, X-ray and antimicrobial studies of 1:1 and 2:1 complexes of silver(I) cyanide with alkanediamine ligands

Several complexes of AgCN with alkanediamine ligands (where the ligands are ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, N,N′-dimethyl-ethylenediamine, N,N′-di-iso-propyl-ethylenediamine, etc.) have been synthesized and structurally characterized. In these species, alkanediamine ligands act as chelating ligands. The X-ray structure of the complex cyano-(N,N′-di-iso-propyl-ethylenediamine)-silver(I) was determined. These complexes have been also characterized by IR, solution as well as solid-state NMR studies. There are two types of IR absorptions observed for mono and dinuclear complexes. For the mono nuclear complexes, a sharp CN band is observed between 2111 and 2131 cm⁻¹ range, whereas for binuclear complexes the bands are in the range 2136-2140 cm⁻¹. The effect of the size of the ligands as well as their substituents is discussed. The antimicrobial activity studies of AgCN and its complexes show that the former exhibits substantial antibacterial activities compared to its complexes.     

Synthesis and characterization of the 1:1 adducts of copper(I) halides with bidentate N,N′-bis(benzophenone)-1,2-diiminoethane Schiff base: Crystal structures of [Cu(bz2en)2][CuX2] (X = Br, I) complexes

1:1 adducts of N,N′-bis(benzophenone)-1,2-diiminoethane (bz₂en) with copper(I) chloride, bromide and iodide, [Cu(bz₂en)₂][CuX₂] (X = Cl, Br, and I), have been synthesized and the structures of the solid bromide and iodide adducts were determined by X-ray crystallography from single-crystal data. The solid-state structure reveals ionic complexes containing a cation of copper(I) ion coordinated to four nitrogen atoms of two bz₂en molecules (distorted tetrahedron) and a linear dibromocuprate(I) and a di-μ-iodo-diiododicuprate(I) anion for the bromo and iodo adducts, respectively. The bromo adduct structure contains CH?Br intermolecular hydrogen bonds. The complexes are very stable towards atmospheric oxygen in the solid state. The spectral properties of the above complexes are also discussed.     

Syntheses and structures of Ag(I) compounds containing btp ligands

Four new Ag(I) complexes with three different modes of structures were obtained by varying the counteranions , and their structures characterized by single-crystal X-ray diffraction analysis. Compounds 1, 2, and 3 crystalize in the C-centered monoclinic space group C2/m. Compound 4 crystalizes in the monoclinic space group P2₁/c. The crystal structures of these complexes show that the complexes 1, 2, and 3 form ligand-supported dinuclear rings, and the dinuclear units of 1 and 3 are further linked by anions to form one-dimensional polymer, while the complex 4 forms an one-dimensional zigzag chain. The structural differences between 1, 2, 3, and 4 show the influences of the counteranions on the structures of the complexes.     

Tetrameric 1:1 and monomeric 1:3 complexes of silver(I) halides with tri(p-tolyl)-phosphine: A structural and biological study

Silver(I) halides react with tri(p-tolyl)phosphine (tptp, C₂₁H₂₁P) in MeOH/MeCN solutions in 1:1 or 1:3 molar ratios to give complexes of formulae {[AgCl(tptp)]₄} (1) or [AgX(tptp)₃] (X = Cl (2), Br (3), I (4)), respectively. The complexes were characterized by elemental analyses, and FT-IR far-IR, FT-Raman, TG and ¹H, ¹³C, ³¹P NMR spectroscopic techniques. Crystal structures of complexes 2-4 were determined by X-ray diffraction at room temperature (rt). The crystal structure of 1 and 4 was also determined at 100(1) and 140(2) K (lt), respectively. In complex 1 four μ3-Cl ions are bonded with four Ag(I) ions forming a cubane while the coordination sphere of silver(I) ions is completed by one P atom from a terminal tri(p-tolyl)phosphine ligand. In complexes 2-3 one terminal halogen and three P atoms from phosphine ligands form a tetrahedral arrangement around the metal ion. Complexes 1-4 were tested for in vitro cytostatic activity against sarcoma cancer cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (PAH, benzo[a]pyrene) carcinogenesis and against murine leukemia (L1210) and human T-lymphocyte (Molt4/C8 and CEM) cells. The silver(I) complexes 1-4 show strong activity.     

Coordination modes of N-(2-hydroxyphenyl)methyl-bis-(2-pyridylmethyl)amine with copper (I) and (II) halides

The title ligand, N-(2-hydroxyphenyl)methyl-bis-(2-pyridylmethyl)amine, was prepared via a condensation-reduction synthetic route. The compounds, CuCl(C₁₉H₁₉N₃O) and [CuBr(C₁₉H₁₉N₃O)]⁺Br⁻ · 3H₂O, were readily synthesized from the reaction of CuCl or CuBr₂ and the ligand in acetonitrile. The title copper(I) compound is an O-H ? Cl hydrogen-bonded linear chain of tetrahedrally coordinated copper centers, and the title copper(II) compound exists as two strongly tetragonally distorted dibromide bridged metal cations in a dimer with the phenol hydroxyl groups weakly bound in a trans-fashion to one of the bridging bromides. In the copper(I) complex the phenoxy group acts only as a hydrogen bond donor, whereas in the copper(II) complex it acts both as a ligand and a hydrogen bond donor.     

Tunable polymerization of silver complexes with organosulfur ligand: counterions effect, solvent- and temperature-dependence in the formation of silver(I)-thiolate(and/or thione) complexes

The reaction of pyridine-2-thiol with AgBF₄ and AgClO₄ in MeCN gave rise to polymeric compounds [{Ag(HPyS)₂}₂(BF₄)₂]_n (1) and [{Ag(HPyS)₂}₂(ClO₄)₂]_n (2) (HPyS=pyridine-2-thione), respectively, while the similar reaction of pyridine-2-thiol with AgNO₃ resulted in a polymeric compound [{Ag₄(HPyS)₆}(NO₃)₄]_n (3). X-ray single-crystal diffraction analyses showed that the cations of both 1 and 2 possess a single-metal-atom chain structure but that of 3 is a double-metal-atom chain structure. The difference between 1 (or 2) and 3 showed counterion effect in polymerization of silver-thione compounds. In the presence of water, the treatment of pyridine-2-thiol with AgBF₄ in DMF at 0 °C generated a polymeric compound [Ag(SPy)]_n (4) (Spy=pyridine-2-thiolate) with graphite-like layered array of silver ions. Compound 4 can convert into its isomer [Ag₆(SPy)₆]_n (5) through soaking in DMF for 1 month. However, the similar reaction of pyridine-2-thiol with AgBF₄ in MeCN-H₂O (v:v=40:1) at room temperature gave another layered polymeric compound [{Ag₅(Spy)₄(HPyS)}BF₄]_n (6). The preparation of 4, 5, and 6 showed that temperature and solvent exert influence on formation of silver-thiolate polymers. The reaction of AgNO₃ with K₂i-mnt (i-mnt=2,2-dicyanoethene-1,1,-dithiolate) and pyridine-2-thiol gave a polymer [Ag₄(μ₄-i-mnt)₂(μ-HPyS)₂(μ-HPyS)_4/2]_n (7) with one-dimensional (1-D) chain structure consisting of Ag₄ square planar cluster units linked by 1H-pyridine-2-thione ligand. The treatment of AgNO₃ with NaS₂CNEt₂ and pyridine-2-thiol in DMF resulted in another polymeric compound [Ag₄(μ₃-S₂CNEt₂)₂(μ₂-SPy)_4/2]_n (8). The preparation and characterization of these polymeric compounds demonstrated that polymerization of silver(I)-thione and silver(I)-thiolate complexes is tunable through controlling reaction conditions. Semiconducting property studies of 1-8 demonstrated that the electrical conductivity of 4 is 2.04×10⁻⁵ S cm⁻¹ at 25 °C and increases as temperature rises, and those of 1-3 and 5-8 are in the range of 1×10⁻¹²-1×10⁻¹⁵ S cm⁻¹ at room temperature and independent on the temperature, indicating that 1 is a semiconductor and the others are insulators.     

Palladium complexes with PCP ligands.: Preparation and structural studies of two forms of [(PCP)Pd(OH2)]BF4

Abstraction of chloride from the Pd complex {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]PdCl with AgBF₄ in THF gives {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(THF)}⁺BF₄ ⁻. Attemped crystallization of this THF complex produced the aqua complex {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(OH₂)}⁺BF₄ ⁻. Crystal structures of two crystalline forms of this compound are reported. In {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(OH₂)}⁺BF₄ ⁻·THF, one hydrogen of the water is hydrogen bonded to the oxygen of the THF, and the other hydrogen is hydrogen bonded to an F of the BF₄ ⁻ anion. Another crystalline form has no THF, but has both of the hydrogens of water hydrogen bonded to different BF₄ ⁻ anions, such that two different BF₄ ⁻ anions bridge two {[η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]Pd(OH₂)}⁺ cations. A crystal structure is also reported for the palladium chloride complex [η³-2,6-(^tBu₂PCH₂)₂C₆H₃)]PdCl.