共查询到20条相似文献,搜索用时 32 毫秒
1.
John F. Young 《Inorganica chimica acta》2010,364(1):138-143
A Cr(III) triflate coordinated by the bulky β-diketiminate MeLiPr (MeLiPr = 2,4-pentane N,N′-bis(2,6-diisopropylphenyl)diketiminate) was synthesized from the corresponding bridging iodide complex [MeLiPrCr(μ-I)]2 by ligand substitution and subsequent oxidation with silver triflate (AgOTf). MeLiPr CrIII(OTf)2 exhibits rare trigonal bipyramidal geometry about Cr(III). Attempts to alkylate this triflate synthon with 1,4-dilithiobutane (Li(CH2)4Li) led to reduction, while reaction with dimethylzinc (ZnMe2) led to a mono-alkylated product; only the reaction with methyl lithium (MeLi) was successful in generating a dialkyl. 相似文献
2.
Javier Arias 《Inorganica chimica acta》2011,365(1):501-504
The crown ether isocyanide CNR (R = benzo-15-crown-5) reacts with silver(I) salts in the appropriate molar ratio to give [Ag(CNR)n]X (n = 1, 2; X = CF3SO3, BF4). X-ray diffraction studies of [Ag(CF3SO3)(CNR)] show the molecules associated in a dinuclear manner with an antiparallel orientation. The silver centers are tetracoordinated to the isocyanide and to three oxygens, one from the triflate anion and two from the second crown ether in the dimer. The molecular structure displays five cycles: the two 15-crown ether rings, two five-membered argentacycles and a 22-membered diargentacycle. The crown ether in these complexes is able to detect alkaline cations from M(CF3SO3) (M = Li, Na, K) by NMR in d6-acetone solutions, and to distinguish Li+-Na+ from K+. 相似文献
3.
Tianle Zhang Changpeng Ji Dongshuang Hu Chunguang Chen 《Inorganica chimica acta》2007,360(5):1609-1615
A new dimeric silver(I) complex [Ag(PhPPy2)(CH3CN)]2(ClO4)2 (1) (PhPPy2 = bis(2-pyridyl)phenylphosphine) was synthesized by a direct reaction of [Ag(CH3CN)4]ClO4 with ligand PhPPy2. X-ray crystallographical studies revealed that in 1, two silver atoms are bridged by two PhPPy2 ligands and bonded to each other. Each Ag(I) adopts a distorted trigonally bi-pyramidal geometry, and axially coordinated acetonitrile molecules are collinear with two silver atoms. By using 1 as a building block precursor, a 1D coordination polymer, [Ag2(PhPPy2)2(1,3,5-C6H3(CO2)2(CO2H))]∞ (2) was prepared by replacing axially coordinated acetonitrile molecules in 1 with two carboxylate groups of a bridging ligand, 1,3,5-benzenetricarboxylate. In solid state, linear polymeric chains are oriented parallel to each other and interestingly interact by hydrogen bonding through their carboxylic/carboxylate groups to construct a novel wave-shaped 2D network. Both 1 and 2 exhibit similar photoluminescent properties in solid state at room temperature. 相似文献
4.
Okan Zafer Ye?ilel Gökhan Ka?ta? ?nci ?lker Orhan Büyükgüngör 《Inorganica chimica acta》2010,363(8):1849-91
Five new silver(I)-saccharinate complexes [Ag2(sac)2(tmen)2] (1), [Ag2(sac)2(deten)2] (2), [Ag2(sac)2(dmen)2] (3), [Ag(sac)(N,N-eten)] (4), and [Ag(sac)(dmpen)]n (5); (sac = saccharinate, tmen = N,N,N′,N′-tetramethylethylenediamine, deten = N,N′-diethylethylenediamine, dmen = N,N′-dimethylethylenediamine, N,N-eten = N,N-diethylethylenediamine and dmpen = 1,3-diamino-2,2-dimethylpropan) have been synthesized and characterized by elemental analyses, IR, thermal analyses, single crystal X-ray diffraction and antimicrobial activities. The crystallographic analyses show that all the complexes crystallize in monoclinic space group P21/c. In 1, the sac ligand acts as a bridge to connect the silver centres through its imino N and carbonyl O atoms forming an eight-membered bimetallic ring in a chair conformation. Complex 2 has also a dimeric structure in which the monomeric [Ag(sac)(deten)] units are linked by Ag?Ag interactions. In 3, saccharinate ligand acts as a bridging bidentate ligand between two silver(I) centres through sulfonyl group and imino N atom, forming an alternating polymeric chain through the direction [0 1 0]. In 4, the inter-molecular N-H?O hydrogen bonds form one-dimensional polymeric chains through the a axis, and these linear chains are inter-connected to each other by N-H?O hydrogen bonds, which produce a chain of edge-fused and rings along [1 0 0]. Complex 5 is a coordination polymer in which the monomeric [Ag(dmpen)(sac)]n units are linked by Ag?Ag interactions, and the dmpen ligand acts as a bridge between the silver(I) ions, forming a two-dimensional network parallel to the (1 0 0) plane. 相似文献
5.
Three new silver(I) complexes of 5,5-diethlybarbiturate (barb), [Ag(barb)(apy)]·H2O (1), {[Ag(μ-ampy)][Ag(μ-barb)2]}n (2) and [Ag(barb)(dmamhpy)] (3) [apy = 2-aminopyridine, ampy = 2-aminomethylpyridine and dmamhpy = 2-(dimethylaminomethyl)-3-hydroxypyridine] have been synthesized and characterized by elemental analysis and FT-IR. Single crystal X-ray diffraction analyses showed that complexes 1 and 3 are mononuclear. In 1, the silver(I) ion is linearly coordinated by a barb anion and a ampy ligand, while a bidentate dmamhpy ligand together with an N-coordinated barb anion forms a trigonal coordination geometry around silver(I) in 3. Complex 2 is a one-dimensional coordination polymer in which silver(I) ions are bridged by ampy ligands, leading to a cationic chain . The [Ag(barb)2]− units contains two N-bonded barb ligands, bridging the silver centers in the cationic and anionic units via the carbonyl O atoms. Thus, complex 2 contains two-coordinated and four-coordinated silver ions. All complexes display hydrogen-bonded network structures and exhibit appreciable fluorescence at room temperature. Thermal analysis (TG-DTA) data are in agreement with the structures of the complexes. 相似文献
6.
The synthesis of an iron(III) complex [Fe(L)(1-Meim)] (1-Meim = 1-methylimidazole) coordinated by an asymmetric N-capped tripodal tetradentate ligand (L) equipped with three aromatic arms is described. X-ray crystallographic analysis shows that the complex adopts a distorted bipyramidal geometry with a new type of N2O2S coordination environment around the iron centre. 相似文献
7.
Stefanus Otto 《Inorganica chimica acta》2010,363(13):3316-3320
The substitution behaviour of [PtCl(R)(COD)] (R− = Me and Fc) complexes, by the stepwise addition of phosphine ligands, L (L = PPh3, PEt3 and P(NMe2)3), were investigated in situ by 1H and 31P NMR spectroscopy. Addition of less than two equivalents of the phosphine ligand results in the formation of dimeric molecules with the general formula trans-[Pt(R)(μ-Cl)(L)]2 for the sterically demanding systems where R− = Me/L = P(NMe2)3 and R− = Fc/L = PEt3, PPh3 and P(NMe2)3 while larger quantities resulted in cis- and trans mixtures of mononuclear complexes being formed. In the case of the relatively small steric demanding, strongly coordinating, PEt3 ligand the trans-[PtCl(R)(PEt3)2] mononuclear complexes were exclusively observed in both cases. The crystal structures of the two substrates, [PtCl(R)(COD)] (R− = Me or Fc), as well as the cis-[PtCl(Fc)(PPh3)2] substitution product are reported. 相似文献
8.
Robert M.K. Deng Keith B. Dillon Andrés E. Goeta Helena J. Shepherd 《Inorganica chimica acta》2009,362(14):5109-2424
The complexes [Cd(dipyr)2(sac)(H2O)] sac·H2O 1 and [Hg(dipyr)(sac)2] 2, where dipyr = dipyridylamine and sac = saccharinate, have been synthesised, and fully characterised by single-crystal X-ray diffraction at 120 K. The geometry around Cd in 1 is approximately octahedral, with the metal coordinated by two bidentate dipyr ligands, one N-bonded sac and one H2O molecule; the second sac forms the counter-ion, and there is also a water of crystallisation. An extensive H-bonded network is formed. In the anhydrous Hg complex 2, the metal has approximately tetrahedral geometry, with coordination from a bidentate dipyr ligand and two N-bonded sac groups. H-bonding interactions are again extensive, even without the presence of H2O molecules in the structure, leading to chains along the a-axis. 相似文献
9.
Yusaku Suenaga Kouzou KitamuraTakayoshi Kuroda-Sowa Masahiko MaekawaMegumu Munakata 《Inorganica chimica acta》2002,328(1):105-110
Silver(I) complexes of hexakis(tolylsulfanyl)benzene (htsb), [Ag(htsb)](PF6) (1), have been prepared and their molecular structures were determined by X-ray crystallography. In 1, the silver ion prefers a square planar coordination geometry comprized of four S atoms from two different htsb molecules and producing a zigzag chain structure of AgS in the silver coordination polymer. Based on the thermo-gravimetry analysis results, two tolylsulfanyl groups were easily eliminated at approximately 211 °C. However, [Ag(htsb)(2-butanone)] (PF6) (2), which were obtained by the reactions in different solvents, showed a different colors and thermal degradation behaviors. 相似文献
10.
David Parker 《Inorganica chimica acta》2007,360(1):203-211
New CuII and NiII complexes of potentially tridentate N2O Schiff base ligands 1 and 2 have been synthesised and characterised. [Cu(2)(OH2)]+ possesses a square planar geometry in the solid state whereas [Ni(1)2] possesses a distorted octahedral geometry in which the amine donors of 1 coordinate weakly to the NiII centre. EPR spectroscopy demonstrates that the N2O2 coordination sphere of [Cu(2)(OH2)]+ is retained in CH2Cl2 solution. [Cu(2)(OH2)]+ exhibits a reversible one electron oxidation at E1/2 = 0.54 V versus [Fc]+/[Fc], the product of which has been characterised by UV-Vis absorption and EPR spectroscopies. The spectroscopic signature of the oxidised product is consistent with the formation of a stable phenoxyl radical ligand bound to a CuII centre. [Ni(1)2] possesses a reversible metal-based oxidation process at E1/2 = 0.03 V versus [Fc]+/[Fc] and a further oxidation, attributed to the generation of a phenoxyl radical centre, at = 0.44 V versus [Fc]+/[Fc]. UV-Vis absorption and EPR spectroscopic studies indicate that the lower potential process is a formal NiIII/II couple. In contrast, the pro-ligands 1H and 2H exhibit chemically irreversible oxidation processes at = 0.42 and 0.40 V versus Fc+/Fc, respectively, and do not support the formation of stable phenoxyl radical species. 相似文献
11.
Claudio Mendicute Fierro Paul D. Smith Simon J. Coles 《Inorganica chimica acta》2006,359(7):2321-2327
The reaction of [Ni(eftp)] [eftp = N,N-ethylene(6-formyl-4-methyliminatothiophenolato)] with hydroxylamine hydrochloride in the presence of potassium acetate in MeOH resulted in the formation of [Ni(L)2], L = 2-mercapto-5-methyl-3-({2-[(5-methyl-benzo[d]isothiazol-7-ylmethylene)-amino]-ethylimino}-methyl)-benzonitrile. A single-crystal X-ray diffraction structural determination showed that the oxime groups of the proposed new binucleating ligand had reacted to produce a nitrile and an isothiazole ring, while two ligand molecules combined with one Ni(II) ion to form a new complex with a cis-S2N2 square-planar geometry. Also, the reaction of 2,6-diformyl-4-methylphenyl disulfide with hydroxylamine in MeCN resulted in the synthesis of 5-methyl-2-oxy-benzo[d]isothiazole-7-carbaldehyde oxime, where an isothiazole ring had formed via the cleavage of the disulfide bond. Again, a single-crystal X-ray diffraction study confirmed the presence of a benzisothiazole product. 相似文献
12.
Mitsushiro Nomura 《Inorganica chimica acta》2010,363(14):3647-2727
The molecular structures of [CpCo(tdt)] and [CpCo(Cl3bdt)] were determined by X-ray diffraction studies. [CpCo(tdt)] was monomeric in the crystal, coordinatively unsaturated with 16-electrons and had a two-legged piano-stool geometry. [CpCo(Cl3bdt)] was dimeric, coordinatively saturated with 18-electrons and became a three-legged piano-stool geometry. There were two crystallographically independent molecules in [CpCo(tdt)] and both molecules were associated with intermolecular Cp?Cp face-to-face interaction. Some intermolecular Co?S interactions were also observed between the crystallographically identical molecules of [CpCo(tdt)]. The cyclic voltammograms of [CpCo(tdt)] and [CpCo(Cl2bdt)] exhibited single oxidation waves, but those of [CpCo(Cl3bdt)] and [CpCo(Cl4bdt)] showed two oxidation waves due to both the monomer and dimer in the solutions. Electrochemical oxidations of these monomers occurred dimerizations by EC reactions in the solutions, and the oxidized dimers could be rereduced to form the original monomers by EC reactions. Spectroelectrochemical data using OTTLE supported the reversible ECEC reactions. Abbreviations of dithiolene ligands are as follows: tdt = toluene-3,4-dithiolate, Cl2bdt = 3,6-dichlorobenzene-1,2-dithiolate, Cl3bdt = 3,4,6-trichlorobenzene-1,2-dithiolate, and Cl4bdt = tetrachlorobenzene-1,2-dithiolate. 相似文献
13.
Shu Qin Liu Takayoshi Kuroda-Sowa Yusaku Suenaga Megumu Munakata 《Inorganica chimica acta》2005,358(4):919-926
Coordination polymers of [2.2]paracyclophane (pcp) with in situ silver(I) perfluoro-dicarboxylates characterized by single crystal X-ray analysis are described. Structures are found to strongly depend on the dicarboxylate spacer (n). With disilver(I) tetrafluorosuccinate ((CF2)n(COOAg)2, n = 2), 3D network with composition of [Ag4(pcp)(C2F4(CO2)2)2] (1) forms in which silver salts afford infinite double chains and pcp act as linkages between chains. Changing the silver salt to disilver hexafluoroglutarate ((CF2)n(COOAg)2, n = 3) produces 3D pillared-layer structure of composition of [Ag4(pcp)(C3F6(CO2)2)2] · THF (2) (THF = tetrahydrofuran), in which silver salts form 2D sheets and pcp act as pillars between the sheets. With silver octafluoroadipate (HO2C(CF2)nCO2Ag, n = 4), 2-fold interpenetrated diamond structure, [Ag2(pcp)2(HO2CC4F8CO2)2]2 · 2toluene (3), is obtained in which silver-anion chains and silver-pcp chains are connected with each other in the perpendicular manner. The three complexes represent unprecedented metal-organic networks of silver(I) multicarboxylates and polycyclic aromatic compounds. Additionally, the effects of the dicarboxylate conformations as well as the solvents on the resulting structures were discussed. 相似文献
14.
The synthesis of an unsymmetrical phenanthroline-based ligand, 2-methyl-9-(3,5-dimethylpyrazolylmethyl)-1,10-phenanthroline (L), and its cupric [Cu(II)] (1) and cuprous [Cu(I)] (2) complexes, are reported. The X-ray structures of each of these Cu complexes show distinct changes in coordination environments consistent with the geometrical preferences of the two oxidation states. In the solid-state, the Cu(II) complex (1) adopts a geometry best described as trigonal bipyramidal, while the Cu(I) complex (2) consists of a single dicationic dimer in which the ligand bridges between two copper ions, separated by 4.26 Å. The two Cu(I) coordination sites differ in 2 with one copper center complexed in a trigonal planar geometry and the other copper in a distorted tetrahedral environment; the latter coordination results from an additional CH3CN ligand. Complex 1 exhibits a reversible redox process at −0.34 V versus Fc/Fc+ in CH3CN, attributable to the Cu2+/Cu+ couple, while the dimeric Cu(I) complex (2) does not display this redox couple on the CV timescale. Over minutes however, complex 1 does oxidize in the presence of dioxygen to 2 in CH3CN. 相似文献
15.
Self-assembling [Fe(CN)5(NO)]2− and [M(L)]2+ (M = Ni, Cu; L = macrocycles) led to one-dimensional coordination polymers, [Ni(L1)][Fe(CN)5(NO)] · 2H2O (1) with parallel chains and [Cu(L2)][Fe(CN)5(NO)] · 3H2O (2) exhibiting a slanted chain structure. Compound 1 contains a planar macrocycle L1 coordinated to a slightly distorted octahedral Ni(II) ion in which the planarity of L1 gives rise to piling up chains in parallel. In contrast, a more flexible macrocyclic ligand L2 in 2 that surrounds a Cu center with a tetragonal elongation has bulky cyclohexyl groups together with pendant methyl side groups. The presence of the methyl groups on L2 in a chain makes the cyclohexyl groups in an adjacent chain tilted against the CuN4 basal plane with the methyl groups, eventually resulting in the slanted chain structure. Magnetic data demonstrate that antiferromagnetic interactions (J ≈ −0.13 cm−1) are operating although the paramagnetic centers are linked by the long diamagnetic [Fe(CN)5(NO)]2− anion. 相似文献
16.
Rafael A. Adrian 《Inorganica chimica acta》2008,361(5):1261-1266
Two palladium(II) complexes, [Pd(phen)(NCCH3)2][O3SCF3]2 (1) and [Pd(phen)(μ-OH)]2[O3SCF3]2 · 2H2O (2) (where phen = 1,10-phenanthroline), have been crystallized following the reaction of Pd(phen)Cl2 with silver triflate, Ag(O3SCF3), in acetonitrile and water, respectively. The structures of both complexes are based on a Pd(phen)2+ metal core, with two acetonitrile molecules binding in a monodentate fashion in complex 1 and two hydroxo bridges holding together two cores to form a dimer in complex 2. Additionally, both complexes present a hydrogen bonded 3-D network involving the triflate anions in 1, and water and triflate anions in 2. Both complexes have been characterized by infrared and 1H NMR spectroscopy and their crystal structures determined by X-ray crystallography. 相似文献
17.
In this paper, we report four phosphorescent Cu(I) complexes of [Cu(OP)(PPh3)2]BF4, [Cu(Me-OP)(PPh3)2]BF4, [Cu(OP)(POP)]BF4, and [Cu(Me-OP)(POP)]BF4 with oxadiazole-derived diimine ligands, where OP = 2-(5-phenyl-[1,3,4]oxadiazol-2-yl)-pyridine, Me-OP = 2-(5-p-tolyl-[1,3,4]oxadiazol-2-yl)-pyridine, POP = bis(2-(diphenylphosphanyl)phenyl) ether, and PPh3 = triphenylphosphane, including their synthesis, crystal structures, photophysical properties, and electronic nature. The Cu(I) center has a distorted tetrahedral geometry within the Cu(I) complexes. Theoretical calculation reveals that all emissions originate from triplet metal-to-ligand-charge-transfer excited state. It is found that the inter-molecular sandwich structure triggered by inter- and intra-molecular pi-stacking within solid state Cu(I) complexes is highly effective on restricting the geometric relaxation that occurs in excited states, and thus greatly enhances the photoluminescence (PL) performances, including PL quantum yield improvement, PL decay lifetime increase, and emission blue shift. 相似文献
18.
Brajagopal Samanta Shyamapada Shit Paul Jensen Samiran Mitra 《Inorganica chimica acta》2007,360(7):2471-2484
Four new coordination complexes, NiII(L)2 (1), [CoIII(L)2]ClO4 (2), [Zn(HL)(L)]ClO4 · H2O (3) and [Zn(L)2][Zn(L)(HL)]ClO4 · 7H2O (4) (where L is a monoanion of a Schiff base ligand, N′-[(2-pyridyl)methylene]salicyloylhydrazone (HL) with NNO tridentate donor set), have been synthesised and systematically characterised by elemental analysis, spectroscopic studies and room temperature magnetic susceptibility measurements. Single crystal X-ray diffraction analysis reveals that 1 is a neutral complex, while 2-4 are cationic complexes. Among them, 4 is a rare type of cationic complex with two molecules in the asymmetric unit. The ligand chelates the metal centre with two nitrogen atoms from the pyridine and imino moieties and one oxygen atom coming from its enolic counterpart. All the reported complexes show distorted octahedral geometry around the metal centres, with the two metal-N (imino) bonds being significantly shorter than the two metal-N (Py) bonds. 相似文献
19.
Reaction of copper(I) chloride or bromide with equimolar amounts of the diphos ligand cis-1,2-bis(diphenylphosphino)ethylene (dppet) and a heterocyclic thione (L) in acetonitrile/methanol solvent afforded mononuclear complexes of the type [CuX(dppet)(L)] with the diphosphine ligand acting as a chelating ligand. However, the same reaction carried out at higher temperatures proceeds, in some cases, with exclusion of the phosphine ligand from the coordination sphere leading to double-S-bridged dimers. In contrast, copper(I) iodide under the same conditions gave the thione-free dimeric compound [CuI(dppet)]2 which contains double-bridging iodine atoms. A notable exception was for the reaction with 5-methyl-1,3,4-thiadiazole-2-thione (mtdztH) which, under the same conditions, gave rise to the unexpected, simultaneous formation of the monomer [CuI(dppet)(CH3CN)] as well as the above mentioned dimeric [CuI(dppet)]2. Furthermore treatment [CuX(dppet)(L)] with two equivalents of triphenylphosphine was found to cause replacement of the diphos ligand, while substitution of the chlorine atom under HCl elimination and formation of [Cu(dppet)(mftztH)2] occured in the unique case of treating [CuCl(dppet)(mftztH)] with one additional equivalent of the same thione ligand. The structures of one representative for each of the above mentioned types of complexes, namely [CuBr(dppet)(mftztH)], [Cu(dppet)(mftztH)2], [Cu(μ-I)(dppet)]2 · [CuI(dppet)(CH3CN)] and [CuBr{μ-S(pymtH)}(pymtH)]2 have been established by single-crystal X-ray diffraction. 相似文献
20.
Fabrice Pointillart 《Inorganica chimica acta》2008,361(1):373-379
The reaction of [Ag4(hfac)4(THF)2] (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate, THF = tetrahydrofurrane) with 2,2′-bipyrimidine (bpm) leads to single crystals. They crystallise in the triclinic system, space group . Their structure consists of [Ag4(hfac)4(μ2-bpm)3] tetranuclear complexes. In this complex, Ag(I) ions adopt distorted square planar and trigonal prismatic geometries. When [Ag4(hfac)4(THF)2] is replaced by monohydrated silver(I) perchlorate, a one-dimensional (1D) compound with a formula of [[Ag(μ2-bpm)]+]n, is obtained as single crystals. They crystallise in the monoclinic system, space group P21/c. Their structure consists of [[Ag(μ2-bpm)]+]n chains separated by non-coordinated perchlorate ions. In the chains, the Ag(I) centres adopt a square planar geometry. Finally, starting from [[Ag(μ2-bpm)]+]n, and sodium oxalate , another 1D compound with a formula of [Ag(μ2-bpm)(μ2-ox)]n, 4nH2O is obtained as single crystals. They crystallise in the triclinic system, space group . In these chains, bipyrimidine and oxalate are alternate. They generate a square planar geometry around the Ag(I) cations. 相似文献