共查询到20条相似文献,搜索用时 23 毫秒
1.
Ali Canlier 《Inorganica chimica acta》2010,363(1):1-4850
Crystal structure of [ReO2(4-MeOpy)4][PF6] (4-MeOpy = 4-methoxypyridine) complex has been examined by the single crystal X-ray analytical method. This complex shows a trans-dioxo geometry (average Re-O bond length = 1.766(2) Å) and its equatorial plane is occupied by four 4-MeOpy molecules (average Re-N bond length = 2.156(4) Å). Electrochemical reaction of [ReO2(4-MeOpy)4]+ in CH3CN solution containing tetra-n-butylammonium perchlorate as a supporting electrolyte has been studied using cyclic voltammetry at 24 °C. Cyclic voltammograms show one redox couple around 0.65 V (Epa) and 0.58 V (Epc) [versus ferrocene/ferrocenium ion redox couple, (Fc/Fc+)]. Potential differences between two peaks (ΔEp) at scan rates in the range from 0.01 to 0.10 V s−1 are 65 mV, which is almost consistent with the theoretical ΔEp value (59 mV) for the reversible one electron transfer reaction at 24 °C. The ratio of anodic peak currents to cathodic ones is 1.04 ± 0.03 and the (Epa + Epc)/2 value is constant, 0.613 ± 0.001 V versus Fc/Fc+, regardless of the scan rate. Spectroelectrochemical experiments have also been carried out by applying potentials from 0.40 to 0.77 V versus Fc/Fc+ with an optically transparent thin layer electrode. It was found that the UV-visible absorption spectra show clear isosbestic points at 228, 276, and 384 nm, and that the electron stoichiometry is evaluated as 1.03 from the Nernstian plot. These results indicate that the [ReO2(4-MeOpy)4]+ complex is oxidized reversibly to the [ReO2(4-MeOpy)4]2+ complex. Furthermore, it was clarified that the [ReO2(4-MeOpy)4]2+ in CH3CN has the characteristic absorption bands at 236, 278, 330, 478, and 543 nm and their molar absorption coefficients are 4.3 × 104, 4.5 × 103, 1.0 × 104, and 6.1 × 103 M−1 cm−1 (M = mol dm−3), respectively. 相似文献
2.
Reaction of [Ru2(O2CMe)4]Cl with K3[Cr(CN)5NO] in water forms Hx[RuII/III2(O2CMe)4]3−x-[Cr(CN)5NO]·zH2O (x = 0.2) that magnetically orders at 4.0 K and possesses an interpenetrating body centered cubic [a = 13.2509(2) Å] structure with random locations of the bridging nitrosyl ligands, and x/3 vacant cation sites. Similarly, the aqueous reaction of [Ru2(O2CMe)4]Cl with Na2[Fe(CN)5NO] forms paramagnetic [Ru2(O2CMe)4]2[Fe(CN)5NO]·H2O, which has a similar tetragonal interpenetrating structure [a = 13.0186(1) Å, c = 13.0699(2) Å] where the NO ligands are presumably nonbridging and 1/3 of the expected cation sites are unoccupied. The presence of uncoordinated NO sites in addition to missing neighboring [Ru2(O2CMe)4]+ units, results in significant vacancies (or holes) in the lattice. 相似文献
3.
Konstantinos D. Demadis Edward M. Kober Peter S. White 《Inorganica chimica acta》2007,360(3):1143-1153
Structural changes between [OsIIL3]2+ and [OsIIIL3]3+ (L: 2,2′-bipyridine; 1,10-phenanthroline) and molecular and electronic structures of the OsIII complexes [OsIII(bpy)3]3+ and [OsIII(phen)3]3+ are discussed in this paper. Mid-infrared spectra in the ν(bpy) and ν(phen) ring stretching region for [OsII(bpy)3](PF6)2, [OsIII(bpy)3](PF6)3, [OsII(phen)3](PF6)2, and [OsIII(phen)3](PF6)3 are compared, as are X-ray crystal structures. Absorption spectra in the UV region for [OsIII(bpy)3](PF6)3 and [OsIII(phen)3](PF6)3 are dominated by very intense absorptions (ε = 40 000-50 000 M−1 cm−1) due to bpy and phen intra-ligand π → π∗ transitions. In the visible region, relatively narrow bands with vibronic progressions of ∼1500 cm−1 appear, and have been assigned to bpy or phen-based, spin-orbit coupling enhanced, 1π → 3π∗ electronic transitions. Also present in the visible region are ligand-to-metal charge transfer bands (LMCT) arising from π(bpy) → t2g(OsIII) or π(phen) → t2g(OsIII) transitions. In the near infrared, two broad absorption features appear for oxidized forms [OsIII(bpy)3](PF6)3 and [OsIII(phen)3](PF6)3 arising from dπ-dπ interconfigurational bands characteristic of dπ5OsIII. They are observed at 4580 and 5090 cm−1 for [OsIII(bpy)3](PF6)3 and at 4400 and 4990 cm−1 for [OsIII(phen)3](PF6)3. The bpy and phen infrared vibrational bands shift to higher energy upon oxidation of Os(II) to Os(III). In the cation structure in [OsIII(bpy)3](PF6)3, the OsIII atom resides at a distorted octahedral site, as judged by ∠N-Os-N, which varies from 78.78(22)° to 96.61(22)°. Os-N bond lengths are also in general longer for [OsIII(bpy)3](PF6)3 compared to [OsII(bpy)3](PF6)2 (0.010 Å), and for [OsIII(phen)3](PF6)3 compared to [OsII(phen)3](PF6)2 (0.014 Å). Structural changes in the ligands between oxidation states are discussed as originating from a combination of dπ(OsII) → π∗ (bpy or phen) backbonding and charge redistribution on the ligands as calculated by natural population analysis. 相似文献
4.
Lei Yang 《Inorganica chimica acta》2005,358(15):4505-4510
An organically templated zinc-substituted gallium phosphite, [H3N(CH2)2NH3]1/2 · [GaZn(HPO3)3(H2O)2] was synthesized under mild hydrothermal conditions in the presence of ethylenediamine (en) as structure-directing agent and characterized by single-crystal X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pbcn with unit cell parameters: a = 18.6146(10) Å, b = 11.0454(6) Å, c = 10.9074(4) Å, V = 2242.62(19) Å3 and Z = 8. This compound has a three-dimensional framework built up from secondary building units (SBU) of Ga(III) (or Zn(II)) and HPO3 pseudopyramid by sharing vertices. The structure displays a two-dimensional channel system running along the [0 0 1] and [0 1 0] direction with 5-, 8- and 10-membered rings. The diprotonated ethylenediamine template molecules are located in the channels. In this structure, some of the Ga(III) sites are occupied by Zn(II) atoms. The compound was also characterized by IR spectroscopy, inductively coupled plasma (ICP), X-ray photoelectron spectra (XPS), differential thermal and thermogravimetric analyses. 相似文献
5.
The P,P′diphenylmethylenediphosphinic acid (H2pcp) reacts with Co(ClO4)2 · 6H2O and 4,4′-bipyridine to give a mixture of two polymeric isomers of formula [Co(pcp)(bipy)0.5(H2O)2], {red (1) and pink (2)} and the new violet hybrid [Co(Hpcp)2] (3). The pure red and violet species have been obtained by the reaction of H2pcp with Co(CH3COO)2 · 4H2O and bipy or with Co(ClO4)2 · 6H2O, respectively. The analogous reaction of Ni(CH3COO)2 · 4H2O or Ni(ClO4)2 · 6H2O with H2pcp and bipy affords only the [Ni(pcp)(bipy)0.5(H2O)2] species (4). The two cobalt isomers present different structural arrangements. Whereas the red isomer (1) shows an undulated 2D layered structure, the pink one (2) forms an infinite monodimensional strand. Both the architectures extend to higher dimensions through hydrogen bonding interactions. The nickel derivative is isomorphous with the red cobalt isomer. The violet [Co(Hpcp)2] (3), which is isomorphous with the complexes of the reported series [M(Hpcp)2], M = Ca(II), Mg(II), presents a monodimensional polymeric structure. Compounds 1 and 4 show a very similar thermal behaviour, the two water molecules being lost in the temperature range 25-150 and 160-320 °C, respectively. Temperature dependent X-ray powder diffractometry (TDXD) has been performed on compound 1 in order to follow the structural transformations that occur during the heating process. 相似文献
6.
A new complex of composition [Cu(2-NO2bz)2(nia)2(H2O)2] (1) (nia = nicotinamide, 2-NO2bz = 2-nitrobenzoate) has been prepared and its composition and stereochemistry as well as coordination mode have been determined by elemental analysis, electronic, infrared and EPR spectroscopy, magnetization measurements over the temperature range 1.8-300 K, and its structure has been solved, as well. The complex structure consists of the centrosymmetric molecules with Cu(II) atom monodentately coordinated by the pair of 2-nitrobenzoato anions and by the pair of nicotinamide molecules, forming nearly tetragonal basal plane, and by a pair of water molecules that complete tetragonal-bipyramidal coordination polyhedron about the copper atom. The complex 1 exhibits magnetic moment μeff = 1.86 B.M. at 300 K which decreases to μeff = 1.83 B.M. at 1.8 K. The magnetic susceptibility temperature dependence obeys Curie-Weiss law with Curie constant of 0.442 cm3 K mol−1 and with Weiss constant of −1.0 K. EPR spectra at room temperature as well as at 77 K are of axial type with g⊥ = 2.065 and g∥ = 2.280 and exhibit clearly, but partially resolved parallel hyperfine splitting with AII = 160 G, that is consistent with the determined molecular structure of 1. In order to analyze the factors influencing the degree of tetragonal distortion of coordination polyhedron, the dataset of 72 structures similar to that of 1 was extracted from CCD and analyzed. A significant correlation between the average Cu-Oax bond length and tetragonality parameter τ which was found as a consequence of the Jahn-Teller effect. 相似文献
7.
Two new tetrahedral tungsten cyanide cluster compounds, [Cu(dien)]3[W4Te4(CN)12] · 9H2O (1) (dien=diethylenetriamine) and [Ni(en)(NH3)]3[W4Se4(CN)12] · 7.5H2O (2) (en=ethylenediamine), were synthesized by treating aqueous solutions of the saltlike cluster compound K6[W4Te4(CN)12] · 5H2O/K6[W4Se4(CN)12] · 6H2O with copper(II)/nickel(II) chloride in aqueous ammonia containing dien/en. The cyano-bridged layered coordination polymeric compounds were characterized by single-crystal X-ray diffraction analysis: monoclinic, space group P21 for 1; trigonal, space group for 2. Structures of 1 and 2 consist of infinite neutral layers of cluster components {W4Te4(CN)12}/{W4Se4(CN)12} connected, one another by {Cu(dien)} or {Ni(en)(NH3)} fragments, respectively. 相似文献
8.
Christophe Faulmann Stéphane Dorbes Kane Jacob Gábor Molnár José Antonio Real 《Inorganica chimica acta》2007,360(13):3870-3878
A new compound of formula [Fe(qsal)2][Ni(dmit)2] (1) has been synthesised, structurally and magnetically characterised (qsalH = N-(8-quinolyl)salicylaldimine, dmit2− = 1,3-dithiol-2-thione-4,5-dithiolato). Its structural features and its magnetic behaviour were compared with those of [Fe(qsal)2]-based complexes, and more particularly [Fe(qsal)2][Ni(dmit)2] · 2CH3CN. 相似文献
9.
The crystal structures of [Cr(NO)(NH3)5](PF6)2 (red) and [Cr(NO)(NH3)5]Cl(PF6) (brown) have been determined. The [Cr(NO)(NH3)5]2+(A) complex cations in these compounds have a slightly distorted octahedral geometry with a strictly linear Cr-N-O arrangement (from symmetry). The short interatomic distances (2.399 Å × 4) between the O (nitrosyl) and H (ammonia in adjacent complex cations) atoms in A(PF6)2 indicate the existence of hydrogen bonds, while the interatomic distances (3.258 Å × 8) between those in ACl(PF6) are much longer, and the hydrogen bonds should be weak in spite of the presence of the smaller counter anion of chloride ion in ACl(PF6). Comparisons of the five crystal structures of A(PF6)2, ACl2, ACl(ClO4), ACl(PF6), and A(ClO4)2 have led to the conclusion that the existence of the strong hydrogen bonds gives red crystals of A(PF6)2, while the absence of hydrogen bonds results in the formation of green crystals of A(ClO4)2 (O ? H, 3.595 Å × 2). The color change of the crystals (from red to green) with the change of outer sphere anions is attributed to the change of the strength of the hydrogen bonding between the complex cations. 相似文献
10.
Yuri V. Mironov Konstantin A. Brylev Sung-Jin Kim Svetlana G. Kozlova Vladimir E. Fedorov 《Inorganica chimica acta》2011,370(1):363-368
A hexarhenium cyanohydroxo anionic cluster complex [Re6Se8(CN)4(OH)2]4− was synthesized for the first time starting from [Re6Se8(OH)6]4−, which was crystallized as a salt of the composition Cs2.75K1.25[Re6Se8(CN)4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded [Cu(NH3)5]2[Re6Se8(CN)4(OH)2]·8H2O (2) or [{Cu(CH3NH2)4}2Re6Se8(CN)4(OH)2] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) Å, c = 19.430(2) Å, V = 5938.3(10) Å3); compound 2 is crystallized in the monoclinic space group P21/n with two formula units per cell (a = 12.1845(13) Å, b = 8.6554(9) Å, c = 19.2568(19) Å, β = 91.081(2)°, V = 2030.5(4) Å3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) Å, b = 14.611(3) Å, c = 13.751(3) Å, V = 3981.2(13) Å3). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re6Se8(CN)4(OH)2]4− was elucidated by DFT calculations. 相似文献
11.
Jae-Hyuk Her Peter W. Stephens Bretni S. Kennon Joel S. Miller 《Inorganica chimica acta》2010,364(1):172-175
Reaction of [Ru2(O2CMe)4]Cl and K2[Ni(CN)4] forms [Ru2(O2CMe)4]2[Ni(CN)4] with the targeted layered structure possessing Ru-NCNi linkages, albeit strained, with Ru-NC and Ni-CN angles in the range of 147-167°. The magnetic properties of [Ru2(O2CMe)4]2[Ni(CN)4] can be fit to a zero-field splitting model with D/kB = 95 K (66 cm−1). 相似文献
12.
Two new ruthenium complexes [Ru(bpy)2(mitatp)](ClO4)21 and [Ru(bpy)2(nitatp)](ClO4)22 (bpy = 2,2′-bipyridine, mitatp = 5-methoxy-isatino[1,2-b]-1,4,8,9-tetraazatriphenylene, nitatp = 5-nitro-isatino[1,2-b]-1,4,8,9-tetraazatriphenylene) have been synthesized and characterized by elemental analysis, 1H NMR, mass spectrometry and cyclic voltammetry. Spectroscopic and viscosity measurements proved that the two Ru(II) complexes intercalate DNA with larger binding constants than that of [Ru(bpy)2(dppz)]2+ (dppz = dipyrido[3,2-a:2′,3′-c]phenazine) and possess the excited lifetime of microsecond scale upon binding to DNA. Both complexes can efficiently photocleave pBR322 DNA in vitro under irradiation. Singlet oxygen (1O2) was proved to contribute to the DNA photocleavage process, the 1O2 quantum yields was determined to be 0.43 and 0.36 for 1 and 2, respectively. Moreover, a photoinduced electron transfer mechanism was also found to be involved in the DNA cleavage process. 相似文献
13.
Benjamin G. Harvey 《Inorganica chimica acta》2010,363(1):221-224
Refluxing WCl4(PMe3)3 under a nitrogen atmosphere in the presence of two equivalents of sodium amalgam leads to a reduction to the W(II) complex [cis,mer-WCl2(PMe3)3]2N2 (1), which can be converted to [mer,trans-WCl3(PMe3)2]2N2 (2) via appropriate oxidation/chlorination. Structural data have been obtained for both complexes, and demonstrate significantly increased steric crowding in 1 due to PMe3/PMe3 interactions. The N-N bond distances in the two compounds are similar, at 1.279(4) and 1.243(18) Å, respectively. 相似文献
14.
Encapsulation of [Mn(bpy)3] cations in 2D [Mn(dca)3] sheet: Synthesis, X-ray structure and EPR study
The reaction of Mn(NO3)2 · 4H2O, 2,2′-bipyridine (bpy) and sodium dicyanamide (dca) in aqueous medium yielded the {[Mn(bpy)3][Mn(dca)3]2}n (1). The single-crystal X-ray analysis of 1 revealed that the anionic part of the complex, [Mn(dca)3]−, features infinite 2D sheets with a honeycomb-like porous structure having a void space of ca. 12 Å in which [Mn(bpy)3]2+ cations are encapsulated to yield a fascinating molecular assembly. MnII ions possess an octahedral geometry both in the anionic and cationic components of complex 1. In the anionic component, each MnII ion is bridged by three pairs of dicyanamide anions in an end-to-end fashion with two other MnII ions from adjacent [Mn(dca)3]− moieties. This type of linking propagates parallel to the bc crystallographic plane to form 2D sheets. [Mn(bpy)3]2+ is found to have somewhat “squeezed” upon encapsulation. No measurable magnetic interaction was evidenced through variable temperature magnetic susceptibility measurements. However, in addition to the broad g ≈ 2 resonance typical of magnetically diluted [Mn(bpy)3]2+ cations, EPR spectroscopy evidenced exchange narrowing of the [Mn(dca)3]− resonance at g ≈ 2 thus indicating operation of weak magnetic interactions extended over the whole 2D network through the dca− bridges. 相似文献
15.
One-pot reaction between MnCl2·4H2O, K2tcpd (tcpd2− = [C10N6]2− = (C[C(CN)2]3)2− = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion) and 2,2′-bipyrimidine (bpym = C8H6N4) in aqueous solution yields the new compound [Mn2(bpym)3(tcpd)2(H2O)2] (1). The molecular structure of 1 consists of a centrosymmetrical binuclear complex which includes unprecedented unidentate tcpd ligands with two bidentate and a bis-chelate bpym units. Examination of the intermolecular distances reveals that the dinuclear units are held together by hydrogen bonds involving coordinated water molecules and two nitrile groups of the tcpd ligand, giving rise to a 2D structure overall. Variable-temperature magnetic susceptibility data show the occurrence of slight antiferromagnetic coupling (J = −0.58 cm−1) between the Mn(II) ions through bridging bpym (the exchange Hamiltonian being defined as ). 相似文献
16.
Junhua LuoMaochun Hong Changzhang ChenMaoxiang Wu Dongshou Gao 《Inorganica chimica acta》2002,328(1):185-190
Two new heterometallic complexes, [Cu(en)(H2O)]2[Fe(CN)6]·4H2O (1) and [Cu(en)2][KFe(CN)6] (2), have been isolated from the reactions of CuCl2 and en with K3[Fe(CN)6] in different molar ratios. Both complexes have been characterized by X-ray analyses, IR spectra and elemental analyses. Complex 1 is a cyanide bridged bimetallic assembly, its crystal structure consists of a two-dimensional polymeric sheet with two different rings, one a four-membered square ring and another a 12-membered hexagonal ring. The Fe(II) ion of 1 has two terminal, two linear bridging and two 1,1 en-on bridging cyanide groups. In the crystal structure of 2, the neighboring [Fe(CN)6]3− units are bridged by the K+ and the [K[Fe(CN)6]]2− units forming a three-dimensional network structure. The [Cu(en)2]2+ units fill in the holes of the network acting as counter cations and charge compensations. Variable temperature magnetic susceptibility studies of 1 indicate that the complex exhibits ferromagnetic interaction between the Cu(II) ions. 相似文献
17.
The compounds W(CO)5P(C6H4-4-CH2CH2(CF2)7CF3)3 (1) and W(CO)5P(CH2CH2(CF2)5CF3)3 (2) were synthesized in order to probe the electronic and physical effects of ligation by perfluorocarbon substituted tertiary phosphine ligands in a W(CO)5L complex. The π-accepting ability of the fluorous phosphines was found to rank with non-fluorous comparators as P(CH2CH2(CF2)5CF3)3 > P(C6H4-4-CH2CH2(CF2)7CF3)3 > PPh3 > P(p-tolyl)3 > P(n-octyl)3. The X-ray crystal structure of W(CO)5P(C6H4-4-CH2CH2(CF2)7CF3)3 shows strong intermolecular association of fluorous components but confirms that the para fluorocarbon subtituents have an insignificant effect on the tungsten coordination environment. Partition coefficients (toluene/perfluoromethylcyclohexane) were measured for compounds 1 and 2. 相似文献
18.
G. Pivoriunas 《Inorganica chimica acta》2005,358(14):4301-4306
The reaction of [HRe3(CO)12]2− with an excess of Ph3PAuCl in CH2Cl2 yields [(Ph3PAu)4Re(CO)4]+ as the main product, which crystallizes as [(Ph3PAu)4Re(CO)4]PF6 · CH2Cl2 (1 · CH2Cl2) after the addition of KPF6.The crystal structure determination reveals a trigonal bipyramidal Au4Re cluster with the Re atom in equatorial position.If [(Ph3PAu)4Re(CO)4]+ is reacted with PPh4Cl, a cation [Ph3PAu]+ is eliminated as Ph3PAuCl, and the neutral cluster [(Ph3PAu)3Re(CO)4] (2) is formed.It combines with excess [(Ph3PAu)4Re(CO)4]+ to afford the cluster cation, [(Ph3PAu)6AuRe2(CO)8]+. It crystallizes from CH2Cl2 as[(Ph3PAu)6AuRe2(CO)8]PF6 · 4CH2Cl2 (3 · 4CH2Cl2). In [(Ph3PAu)3Re(CO)4] the metal atoms are arranged in form of a lozenge while in [(Ph3PAu)6AuRe2(CO)8]+ two Au4Re trigonal bipyramids are connected by a common axial Au atom.The treatment of [(Ph3PAu)4Re(CO)4]+ with KOH and Ph3PAuCl in methanol yields the cluster cation [(Ph3PAu)6Re(CO)3]+, which crystallizes with from CH2Cl2 as [(Ph3PAu)6Re(CO)3]PF6 · CH2Cl2 (4 · CH2Cl2). The metal atoms in this cluster form a pentagonal bipyramid with the Re atom in the axial position. 相似文献
19.
Ludovic Chahen 《Inorganica chimica acta》2005,358(12):3417-3422
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes. 相似文献
20.
The 2-D K(I)-tetrazole metal-organic complex, [K2(4-TPA)2(H2O)2]n (1), which is constructed by the [K2O4N]n inorganic skeleton chains bridged by the 4-TPA linkers, has been synthesized and characterized by single crystal X-ray crystallography and temperature-dependence dielectric constant(ε) measurement under the alternating electric field, (4-TPA = 2-(4-(1H-tetrazol-5-yl)pyridinium-1-yl) acetate). The ε of temperature dependence remains unchanged almost within the measured temperature range of 90 K to 430 K at 1 M Hz, and the ε of frequency dependence shows a significant decline from 6.7 to 4.6 within the measured frequency range of 200-1 MHz at room temperature. And it is consistent with the low dielectric loss (ε2/ε1) behavior, which is attributed to the highly ordered polarization mechanism. 相似文献