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1.
The dissolution of [(CH3)N]2Na[MnN(CN)5]·H2O in water results in the dissociation of the labile trans-CN ligand to form [MnN(H2O)(CN)4]2−(aq). The formed aqua complex reacts rapidly with a number of nucleophiles such as NCS− and N3−. Here we report the single crystal X-ray structure of the reaction products of as well as the equilibrium and kinetic behaviour of [MnN(H2O)(CN)4]2− in solution. 相似文献
2.
Zhan Shi 《Journal of solid state chemistry》2003,172(2):464-470
A novel compound, [HN(C2H4)3N][(VO)2(HPO3)2(OH)(H2O)]·H2O, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. This compound crystallizes in the monoclinic system with the space group C2/c and cell parameters a=11.0753(3) Å, b=17.8265(6) Å, c=16.5229(5) Å, and β=92.362(2)°. The structure of the compound consists of vanadium phosphite layers which are built up from the infinite one-dimensional chains of [(VO)(H2O)(HPO3)2]2− of octahedral VO5(H2O) and pseudo pyramidal [HPO3], and bridging binuclear fragments of [VO(OH)]2. Thermogravimetric analysis and magnetic susceptibility data for this compound are given. 相似文献
3.
A series of novel octahedral nickel(II) dithiocarbamate complexes involving bidentate nitrogen-donor ligands (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine) or a tetradentate ligand (cyclam = 1,4,8,11-tetraazacycloteradecane) of the composition [Ni(BzMetdtc)(phen)2]ClO4 (1), [Ni(Pe2dtc)(phen)2]ClO4 (2), [Ni(Bzppzdtc)(phen)2]ClO4 · CHCl3 (3), [Ni(Bzppzdtc)(phen)2](SCN) (4), [Ni(BzMetdtc)(bpy)2]ClO4 · 2H2O (5), [Ni(Pe2dtc)(cyclam)]ClO4 (6), [Ni(BzMetdtc)2(cyclam)] (7), [Ni(Bz2dtc)2(cyclam)] (8) and [Ni(Bz2dtc)2(phen)] (9) (BzMetdtc = N,N-benzyl-methyldithiocarbamate(1-) anion, Pe2dtc = N,N-dipentyldithiocarbamate(1-) anion, Bz2dtc = N,N-dibenzyldithiocarbamate(1-) anion, Bzppzdtc = 4-benzylpiperazinedithiocarbamate(1-) anion), have been synthesized. Spectroscopic (electronic and infrared), magnetic moment and molar conductivity data, and thermal behaviour of the complexes are discussed. Single crystal X-ray analysis of 3 and 8 confirmed a distorted octahedral arrangement in the vicinity of the nickel atom with a N4S2 donor set. They represent the first X-ray structures of such type complexes. The catalytic influence of complexes 2, 3, 6, and 7 on graphite oxidation was studied and discussed. 相似文献
4.
The vaporization of DyI3(s) was investigated in the temperature range between 833 and 1053 K by the use of Knudsen effusion mass spectrometry. The ions DyI2+, DyI3+, Dy2I4+, Dy2I5+, Dy3I7+, and Dy3I8+ were detected in the mass spectrum of the equilibrium vapor. The gaseous species DyI3, (DyI3)2, and (DyI3)3 were identified and their partial pressures determined. Enthalpies and entropies of sublimation resulted according to the second- and third-law methods. The following sublimation enthalpies at 298 K were determined for the gaseous species given in brackets: 274.8±8.2 kJ mol−1 [DyI3], 356.0±11.3 kJ mol−1 [(DyI3)2], and 436.6±14.6 kJ mol−1 [(DyI3)3]. The enthalpy changes of the dissociation reactions (DyI3)2=2 DyI3 and (DyI3)3=3 DyI3 were obtained as ΔdH°(298)=193.3±5.6 and 390.3±13.0 kJ mol−1, respectively. 相似文献
5.
A new cobalt Schiff-base complex, [Co(L)(OH)(H2O)] (where L = [N,N′-bis(2-aminothiophenol)-1,4-bis(carboxylidene phenoxy)butane), was synthesized and its electrochemical and spectroelectochemical properties were investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and thin-layer spectro-electrochemistry in solutions of dimethyl sulfoxide (DMSO) and dichloromethane (CH2Cl2). The [Co(L)(OH)(H2O)] complex displays two well-defined reversible reduction processes with the corresponding anodic waves. The half-wave potentials of the first and second reduction processes were displayed at E1/2 = 0.08 V and E1/2 = −1.21 V (scan rate: 0.100 Vs−1) in DMSO, and E1/2 = −0.124 V and E1/2 = −1.32 V (scan rate: 0.100 Vs−1) in CH2Cl2. The potentials of the reduction processes in DMSO are shifted toward negative potentials (0.220–0.112 V) compared to those in CH2Cl2. The electrochemical results are assigned to two one-electron reduction processes; [Co(III)L] + −e → [Co(II)L]− and [Co(II)L]− + −e → [Co(I)L]2−. The six-coordination of the complex remains unchanged during the reduction processes and the electron transfer processes were not followed by a chemical reaction upon scan reversal. It was also seen that [Co(L)(OH)(H2O)] was reduced at a more positive potential than the corresponding salen analogs. The shift and reversibility are apparently related to the high degree of electron delocalization of the [Co(L)(OH)(H2O)] complex, having a N2O2S2 donor set and two additional benzene units. Additionally, in situ spectroelectrochemical measurements support Co(III)/Co(II) and Co(II)/Co(I) reversible reduction processes with the observation of the corresponding spectral changes with the applied potentials Eapp = −0.40 and −1.60 V. Application of the spectroelectrochemical results allowed the determination ofE1/2 and n (the number of electrons) from the spectra of the fully oxidized and reduced species in one unified experiment as well. The results obtained by this method are in agreement with those by the CV and DPV methods. 相似文献
6.
The new manganese tetraphosphonate, Mn[(HO3PCH2)2N(H)(CH2)4(H)N(CH2PO3)2] (1) was hydrothermally synthesized from MnCl2 and N,N,N′,N′-tetrametylphosphono-1,4-diaminobutane, (H2O3PCH2)2N-(CH2)4-N(CH2PO3H2)2. The structure was determined from single-crystal X-ray diffraction data (Mn[(HO3PCH2)2N(H)(CH2)4(H)N(CH2PO3)2], monoclinic, P21/a, with a=9.6663(1), b=9.2249(2), c=10.5452(1) pm, β=105.676(1)°, V=905.35(3)×106 pm, Z=2, R1=0.051, wR2=0.109 (all data). The structure contains the zwitter ions [(HO3PCH2)2N(H)-(CH2)4-(H)N(CH2PO3)2]2− and is built from alternating corner-linked [MnO6] and [PO3C] polyhedra forming a two-dimensional net of eight-rings. These layers are connected to a pillared structure by the diaminobutane groups. Magnetic susceptibility data confirms the presence of Mn2+ ions. Thermogravimetric measurements show a stability of 1 up to ∼290°C. Between 290°C and 345°C a one-step loss of ∼7.0% is observed, and above 345°C the continuous decomposition of the organic part of the structures takes place. 相似文献
7.
Antonio de León Josefina Pons Jordi García-Antón Xavier Solans Mercè Font-Bardía Josep Ros 《Polyhedron》2009
Mononuclear palladium(II) complexes containing a pyrazole-thioether ligand, with general formula trans-[Pd(X)2(bddo)] (X = CN− (1), SCN− (2) or N3− (3); bddo = 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane), have been prepared. Similar reactivity carried out with pyridine or triphenylphosphine has been assayed. When pyridine is used, a mixture of [Pd(bddo)(py)2](BF4)2 ([4](BF4)2) and [Pd(bddo)](BF4)2 is obtained. When triphenylphosphine is used, only [Pd(bddo)](BF4)2 is obtained. The complexes have been characterised by elemental analyses, conductivity measurements, IR and NMR spectroscopies. X-ray crystal structure of trans-[Pd(SCN)2(bddo)] (2) is presented. In this complex the metal atom is coordinated by the two azine nitrogen atoms of the pyrazole rings and two SCN− anions in trans disposition. 相似文献
8.
Alda K.M. Holanda Francisco O.N. da Silva Idalina M.M. Carvalho Alzir A. Batista Javier Ellena Eduardo E. Castellano Ícaro S. Moreira Luiz G.F. Lopes 《Polyhedron》2007
The trans-[Fe(cyclam)(NO)Cl]Cl2 complex was synthesized by the reaction of cis-[Fe(cyclam)Cl2]Cl with NO gas. The X-ray structure of the complex showed that the [Fe–NO] moiety is linear, consistent with the NO+ character of the nitric oxide ligand. This suggestion was reinforced by the IR data, which showed the νNO at 1888 cm−1. The cyclic voltammogram of the trans-[Fe(cyclam)(NO)Cl]2+ complex presented three electrochemical processes at −0.70, 0.08 and 0.40 V versus Ag/AgCl. The first and last redox processes are centered at the NO ligand, whereas the second is characteristic of the generated aqua species, trans-[Fe(cyclam)Cl(H2O)]2+. Upon irradiation at 330 nm, pH 3.4, the title complex releases the NO moiety with the concomitant generation of the trans-[Fe(cyclam)(H2O)Cl]+ complex as suggested by electronic and IR spectroscopy as well as by cyclic voltammetry technique. 相似文献
9.
The N4O3 coordinating heptadentate imidazolidinyl phenolate ligand, H3L (2-(2′-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) forms with Cu(II) a rare aqua bridged complex [{Cu2(μ-L)(μ-H2O)}2](ClO4)2 · 4.5H2O (1 · 4.5H2O). Complex 1 · 4.5H2O contains two crystallographically different but chemically equivalent dinuclear [Cu2(μ-L)(μ-H2O)]+ cationic units in the asymmetric unit. The copper atoms of each dinuclear unit are in a distorted square-pyramidal environment and are held together by phenolate, imidazolidinyl and aqua bridges with a Cu···Cu separation of av. 3.34 Å. The compound exhibits a very weak antiferromagnetic exchange interaction (J = −0.77 cm−1, ? = −2 J?1?2) between the two copper(II) (S = 1/2) ions. The 1H NMR spectrum of the complex shows a total of 17 hyperfine shifted peaks, as expected from the idealized Cs symmetry of the compound, spread over a very large window of chemical shift, spanning about 250 ppm. The complex, having an appropriate intermetallic separation for catechol binding, shows catecholase like activity in MeCN at 25 °C, with the aerobic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylquinone (3,5-DTBQ). 相似文献
10.
The [ReCl3(MeCN)(PPh3)2] complex reacts with bis(pyrazol-1-yl)methane (bpzm) to give [ReCl3(bpzm)(PPh3)]. This compound has been studied by IR, UV–Vis spectroscopy, magnetic measurement and X-ray crystallography. The molecular orbital diagram of [ReCl3(bpzm)(PPh3)] has been calculated with the density functional theory (DFT) method. The spin-allowed triplet–triplet electronic transitions of [ReCl3(bpzm)(PPh3)] have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the title compound has been discussed on this basis. The magnetic behavior is characteristic of a mononuclear d4 low-spin octahedral Re(III) complex (3T1g ground state) and arises because of the large spin–orbit coupling (ζ = 2500 cm−1), which gives a diamagnetic ground state. 相似文献
11.
12.
A high-yield synthesis of trans-RuCl2(CS)(H2O)(PPh3)2 from RuCl2(PPh3)3 and CS2 is described. The coordinated water molecule is labile, and introduction of CNR (R p-toyl or p-chlorophenyl) leads to yellow trans-RuCl2(CS)(CNR)(PPh3)2, which isomerises thermally to colourless cis-RuCl2(CS)(CNR)(PPh3)2. Reaction of AgClO4 with cis-RuCl2(CS)(CNR)(PPh3)2 gives [RuCl(CS)(CNR)(H2O)(PPh3)2]+, from which [RuCl(CS)(CO)(CNR)(PPh3)2]+ and [RuCl(CS)(CNR)2(PPh3)2]+ are derived. Reaction of trans-RuCl2(CS)(H2O)(PPh3)2 with sodium formate gives Ru(η2-O2CH)Cl(CS)(PPh3)2, which undergoes decarboxylation in the presence of (PPh3) to give RuHCl(CS)(PPh3)3. Ru(η2-O2CH)H(CS)(PPh3)2 and Ru(η2-O2CMe)-H(CS)(PPh3)2 are also described. 相似文献
13.
The synthesis, crystal structure and magnetic properties of the cyano-bridged complex [{Cu(cyclam)}3{Fe(CN)6}2] · 6H2O are reported. Its structure is made up of centrosymmetric S-shaped pentanuclear [{Cu(cyclam}3{Fe(CN)6)}2] units, in which three [Cu(cyclam)]2+ units are alternatively bridged by two trans-CN groups of [Fe(CN)6]3− anions and water molecules. The pentanuclear Fe2Cu3 units are held together by two complementary and very weak Fe–CN?Cu1 bonds, forming a rope-ladder chain along the c axis. The compound exhibits a ferromagnetic interaction between the Cu(II) and Fe(III) ions as a consequence of the orthogonality of their magnetic orbitals of σ and π nature, respectively. The magnetic data were fitted to the calculated magnetic susceptibility equation for a pentanuclear model, leading to the following magnetic parameters: J1 = 9.0(3) cm−1, J2 = 3.8(4) cm−1, g = 2.2, θ = −1.2 K. These results show that the interactions through the long Cu–N axial bonds are not so weak as is usually assumed. 相似文献
14.
Pavel Kopel Jiří Kameníček Václav Petříček Aleš Kurečka Božena Kalinska Jerzy Mrozinski 《Polyhedron》2007
Nickel and copper complexes containing 1,3,5-benzenetricarboxylic acid, with a combination of selected N-donor ligands and Schiff bases, of the composition Ni3(bimz)6(btc)2 · 12H2O (1), Ni3(btz)9(btc)2 · 12H2O (2), Ni2(L1)(btc) · 7H2O (3), Ni3(L2)2(Hbtc) · 9H2O (4), Ni2(L3)(btc) · 4H2O (5), Cu2(L4)(btc) · 7H2O (6), [Cu3(pmdien)3(btc)](ClO4)3 · 6H2O (7) and [Cu3(mdpta)3(btc)](ClO4)3 · 4H2O (8); H3btc = 1,3,5-benzenetricarboxylic acid, bimz = benzimidazole, btz = 1,2,3-benztriazole, L1 = 2-[(phenylimino)methyl]phenol, L2 = N,N′-bis-(salicylidene)propylenediamine, L3 = 2-{[(2-nitrophenyl)methylene]amino}phenol, L4 = 2-[(4-methoxy-phenylimino)methyl]phenol, pmdien = N,N,N′,N″,N″-pentamethyldiethylenetriamine, mdpta = N,N-bis-(3-aminopropyl)methylamine, have been synthesized. The complexes have been studied by elemental analysis, IR, UV–Vis spectroscopies, magnetochemical and conductivity measurements and selected compounds also by thermal analysis. The crystal and molecular structure of complex 8 was solved. The complex is trinuclear with btc3−-bridge. The coordination polyhedron around each copper atom can be described as a distorted square with a CuON3 chromophore formed by one oxygen atom of carboxylate and three nitrogen atoms of mdpta. The magnetic properties of 8 have been studied in the 1.8–300 K temperature range revealing a very weak antiferromagnetic exchange interaction with J = −0.56 cm−1 for g = 2.13(9). The antimicrobial activities against selected strains of bacteria were evaluated. It was found that only complex 5 is able to inhibit the growth of Staphylococcus strains. 相似文献
15.
Wansheng You Enbo WangLin Xu Zaiming ZhuYuanpeng Gu 《Journal of Molecular Structure》2002,605(1):41-49
The new molecule based on 12-molybdophosphate acid and dibenzo-18-crown-6, [(H3O)(C20H24O6)]2[HPMo12O40]·C20H24O6·3MeCN·H2O 1, was synthesized in acetonitrile and characterized by elemental analyses, IR, 1H NMR, electrospray mass spectra and single crystal X-ray diffraction, indicating that it contains [(H3O)(dibenzo-18-crown-6)]+ cations, where oxonium ions are out of the planes defined by crown ether oxygen atoms, and disordered PMo12O403− anions with α-Keggin structure where the crystal has high lattice energy so that it is difficult to dissolve it. The crystallographic disorder averages Mo-Mo distances and Mo-Ob/c-Mo angles between the M3 triplets and within the M3 triplet. The interactions between crown ether molecules and oxonium ions are hydrogen-bonding with the O(crown ether)-OH3+ distances of 2.510(10)-2.783(7) Å. The interactions between [(H3O)(dibenzo-18-crown-6)]+ cations and PMo12O403− anions are dominantly electrostatic. The electrical conductivity is <10−7 S.cm−1. 相似文献
16.
Lei Wang 《Journal of solid state chemistry》2004,177(1):80-88
Two organically templated zincophosphites, (C6H14N2)·[Zn3(HPO3)4] and (C4H14N2)·[Zn3(HPO3)4] have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction. (C6H14N2)·[Zn3(HPO3)4] crystallizes in the triclinic space group , with cell parameters, a=9.363(4) Å, b=10.051(4) Å, c=10.051(4) Å, α=85.777(13)°, β=82.091(9)°, and γ=79.783(9)°. (C4H14N2)·[Zn3(HPO3)4] crystallizes in the monoclinic space group P21/c, with cell parameters, a=9.9512(3) Å, b=10.1508(3) Å, c=17.8105(5) Å, and β=95.6510(10)°. Although the two structures are different, they have the same anionic framework compositions of [Zn3(HPO3)4]2−. Their frameworks are built up from strictly alternating ZnO4 tetrahedra and HPO3 pseudo pyramids by sharing vertexes. There exist channels with an eight-membered ring window along the a- and c-axis. Powder X-ray diffraction, IR spectroscopy, 31P MAS solid-state NMR, thermogravimetric and differential thermal analyses were also carried out. 相似文献
17.
Sumanta Kumar Padhi Dipankar Saha Rojalin Sahu Japyesan Subramanian Vadivelu Manivannan 《Polyhedron》2008
Three complexes of composition [CrL(X)3], where L = 4′-(2-pyridyl)-2,2′:6′,2″-terpyridine and X = Cl−, N3−, NCS− are synthesized. They are characterized by IR, UV–Vis, fluorescence, EPR spectroscopic, and X-ray crystallographic studies. Structural studies reveal that the Cr(III) ion is coordinated by three N atoms of L in a meridional fashion. The three anions occupy the other three coordination sites completing the mer-N3Cl3 (1) and mer-N3N3 (2 and 3), distorted octahedral geometry. The Cr–N2 has a shorter length than the Cr–N1 and Cr–N3 distances and the order Cr–N(NCS−) < Cr–N(N3−) < Cr–Cl is observed. They exhibit some of the d–d transitions in the visible and intra-ligand transitions in the UV regions. The lowest energy d–d transition follows the trend [CrLCl3] < [CrL(N3)3] < [CrL(NCS)3] consistent with the spectrochemical series. In DMF, they exhibit fluorescence having π → π∗ character. All the complexes show a rhombic splitting as well as zero-field splitting (zfs) in X-band EPR spectra at 77 K. 相似文献
18.
Energy analysis of metal-metal bonding in [RM-MR] (M = Zn, Cd, Hg; R = CH3, SiH3, GeH3, C5H5, C5Me5)
Krishna K. Pandey 《Journal of organometallic chemistry》2007,692(5):1058-1063
The metal-metal bonds of the title compounds have been investigated with the help of energy decomposition analysis at the DFT/TZ2P level. In good agreement with experiment, computations yield Hg-Hg bond distance in [H3SiHg-HgSiH3] of 2.706 Å and Zn-Zn bond distance in [(η5-C5Me5)Zn-Zn(η5-C5Me5)] of 2.281 Å. The Cd-Cd bond distances are longer than the Hg-Hg bond distances. Bond dissociation energies (-BDE) for Zn-Zn bonds in zincocene −70.6 kcal/mol in [(η5-C5H5)2Zn2] and −70.3 kcal/mol in [(η5-C5Me5)2Zn2] are greater amongst the compounds under study. In addition, [(η5-C5H5)2M2] is found to have a binding energy slightly larger than those in [(η5-C5Me5)2M2]. The trend of the M-M bond dissociation energy for the substituents R shows for metals the order GeH3 < SiH3 < CH3 < C5Me5 < C5H5. Electrostatic forces between the metals are always attractive and they are strong (−75.8 to −110.5 kcal/mol). The results demonstrate clearly that the atomic partial charges cannot be taken as a measure of the electrostatic interactions between the atoms. The orbital interaction (covalent bonding) ΔEorb is always smaller than the electrostatic attraction ΔEelstat. The M-M bonding in [RM-M-R] (R = CH3, SiH3, GeH3, C5H5, C5Me5; M = Zn, Cd, Hg) has more than half ionic character (56-64%). The values of Pauli repulsions, ΔEPauli, electrostatic interactions, ΔEelstat, and orbital interactions, ΔEelstat are larger for mercury compounds as compared to zinc and cadmium. 相似文献
19.
Trinuclear mixed-valence Co(III)-Co(II)-Co(III) complex {CoIII(μ-Sal2MePn)(N3)(μ1,1-N3)}2CoII(H2O)2 (I) was synthesized by the reaction of Co(NO3)2 · 6H2O with the Schiff base ligand H2Sal2MePn condensed from 2,2-dimethylpropylenediamine with salicylaldehyde and characterized by elemental analyses and FT-IR spectroscopy.
The molecular structure of I has been determined from single-crystal X-ray diffraction analysis. In this structure, the N3− anions show both terminal and μ1,1-bridging modes. The terminal Co(III) centers exhibit uniform arrangements of the Schiff-base ligand and N3− anions. 相似文献
20.
A new crystal of Nd3+:Sr3Y2 (BO3)4 with a dimension of Φ 15×30 mm3 was grown by the Czochralski method. The grown crystal was characterized using X-ray diffraction. The absorption and emission spectra of Nd3+:Sr3Y2 (BO3)4 were investigated. The absorption transition at 807 nm has an FWHM of 16 nm. The absorption and emission cross sections are 6.32×10−20 cm2 at 807 nm and 1.07×10−19 cm2 at 1065 nm, respectively. The luminescence lifetime τf is 51.7 μs at room temperature. 相似文献