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1.
The title compound (pipzH2)2Mo2Cl8·4H2O (pipz = piperazine),was isolated from the solution of (morphH)2Mo2Cl6(H2O)2 in HCl 1:1 by addition of (pipzH2)Cl2. This reaction indicates the reversibility of the substitution of chloride ions in Mo2Cl84? by water molecules. (pipzH2)2Mo2Cl8·4H2O crystallizes in the Pbca space group, with a = 15.154(2), b = 13.170(2), c = 12.208(2) Å and Z = 4. The structure was solved by the Patterson method and refined to the unweighted and weighted residuals of 0.050 and 0.048. The crystal structure is built form Mo2Cl84?, (pipzH2)2+ and H2O. The MoMo distance of 2.129(3) Å is the shortest one found in all structurally-characterised Mo2X84? (X = Cl, Br) anions. Four independent MoCl distances are 2.456(3), 2.445(3), 2.463(4) and 2.455(4) Å. The (pipzH22+ exists in a usual chair conformation. There is a network of hydrogen bonds of the type NH?Cl, NH?O, OH?Cl and OH?O between the ions and water molecules. 相似文献
2.
Pt(II) complexes of the types K[Pt(R2SO)X3], NR4[Pt(R2SO)X3] and Pt(R2SO)2Cl2 (where X = Cl or Br) were characterized by multinuclear magnetic resonance spectroscopy (195Pt, 1H and 13C). In 195Pt NMR, the chloro ionic compounds have shown signals between −2979 and −3106 ppm, while the cis disubstituted complexes were observed at higher fields, between −3450 and −3546 ppm. The signal of the compound trans-Pt(DPrSO)2Cl2 was found at higher field (−3666 ppm) than its cis analogue (−3517 ppm), since π-back-donation is considerably less effective in the trans geometry. In 1H NMR, a single signal was observed for the sulfoxide in [Pt(DMSO)Cl3]−, but for the other more sterically hindered ligands, two series of resonances were observed for the protons in α and β positions. The coupling constant 3J(195Pt-1H) are between 15 and 33 Hz. The 13C NMR results were interpreted in relation to the concept of inversed polarization of the π sulfoxide bond. The 2J(195Pt-13C) values vary between 35 and 66 Hz, while a few 3J(195Pt-13C) couplings were observed (13-26 Hz). The crystal structures of five monosubstituted ionic compounds N(n-Bu)4[Pt(TMSO)Cl3], N(Me)4[Pt(DPrSO)Cl3], K[Pt(EMSO)Cl3], K[Pt(TMSO)Br3] · H2O and N(Et)4[Pt(DPrSO)Br3] and one disubstituted complex cis-Pt(DBuSO)2Cl2 were determined. The trans influence of the different ligands is discussed. 相似文献
3.
Yuri V. Mironov Konstantin A. Brylev Spartak S. Yarovoi Hartmut Spies Holger Stephan Gert Bernhard 《Inorganica chimica acta》2006,359(4):1129-1134
Two new octahedral cluster complexes - [Re6S8(3,5-Me2PzH)6]Br2 · 2(3,5-Me2PzH) (1) and [Re6Se8(3,5-Me2PzH)6]Br2 · 2(3,5-Me2PzH) (2), where 3,5-Me2PzH is 3,5-dimethylpyrazole, have been synthesized using reaction of rhenium chalcobromide complexes Cs4[Re6S8Br6] · 2H2O and Cs3[Re6Se8Br6] · H2O, respectively, with molten 3,5-dimethylpyrazole. Both compounds synthesized were characterized by X-ray single-crystal diffraction and chemical analysis, IR and luminescent spectra. 相似文献
4.
The syntheses of (PPh4)2[M(CN)3O(pic)] · nH2O (M = Mo, W; n = 2.5, 4; pic = picolinate anion) as well as (PPh4)2[Mo(CN)4O(apic)] · 3H2O (apic = 2-pyridinecarboxaldehyde) are presented. The salts have been characterised by elemental analysis, IR and UV-Vis spectroscopy, cyclic voltammetry and X-ray crystal structure determination of (PPh4)2[Mo(CN)3O(pic)] · 2.5H2O. The anion in the latter salt is approximately octahedral with O and N donor atoms of pic situated in the trans and cis position to the MoO bond, respectively. The picolinate complexes have the characteristic MLCT bands in the visible spectra with the absorption maxima linearly dependent on the Reichardt’s ET solvent parameter. These complexes are shown to exhibit the strongest solvatochromic effect of all studied tricyanooxo and hexacyano complexes of Mo(IV) and W(IV). The obtained values of E1/2 in these salts [0.333 V (Mo) and 0.018 V (W) in 1,2-C2H4Cl2] were found to be the highest of all [M(CN)3O(LL)]2− type complexes making these salts show reversibility in a remarkable variety of solvents. The oxidation of coordinated apic to pic has been demonstrated by means of electronic spectroscopy. The isolated salts were used to monitor the reaction of [M(CN)4O(H2O)]2− with 2,2′-pyridil in water-ethanol solution. It was found that 2,2′-pyridil disproportionate to Hpic and apic in the first step and the other decomposition products of 2,2′-pyridil postulated in the literature were not observed. 相似文献
5.
The complexes [W(X)Cl3(HO2CC6H4NH-2)] [X = O (1), NPh (2)] have been obtained by reaction of either [WOCl4] or [W(NPh)Cl4(Et2O)] with anthranilic acid {1,2-(NH2)(CO2H)C6H4}, respectively. The X-ray crystal structures reveal pseudo-octahedral metal centres, each with a mer-arrangement of chlorines and a chelating acid/amide ligand derived from anthranilic acid. The acid group of this chelate ligand is trans to either the oxo or organoimido functionality. 相似文献
6.
Nikos Lekkas Achilleas Garoufis Joseph Kobe Edward R.T. Tiekink 《Inorganica chimica acta》2006,359(13):4297-4303
The Pd(II) and Pt(II) complexes with triazolopyrimidine C-nucleosides L1 (5,7-dimethyl-3-(2′,3′,5′-tri-O-benzoyl-β-d-ribofuranosyl-s-triazolo)[4,3-a]pyrimidine), L2 (5,7-dimethyl-3-β-d-ribofuranosyl-s-triazolo[4,3-a]pyrimidine) and L3 (5,7-dimethyl[1,5-a]-s-triazolopyrimidine), [Pd(en)(L1)](NO3)2, [Pd(bpy)(L1)](NO3)2, cis-Pd(L3)2Cl2, [Pd2(L3)2Cl4] · H2O, cis-Pd(L2)2Cl2 and [Pt3(L1)2Cl6] were synthesized and characterized by elemental analysis and NMR spectroscopy. The structure of the [Pd2(L3)2Cl4] · H2O complex was established by X-ray crystallography. The two L3 ligands are found in a head to tail orientation, with a Pd?Pd distance of 3.1254(17) Å. L1 coordinates to Pd(II) through N8 and N1 forming polymeric structures. L2 coordinates to Pd(II) through N8 in acidic solutions (0.1 M HCl) forming complexes of cis-geometry. The Pd(II) coordination to L2 does not affect the sugar conformation probably due to the high stability of the C-C glycoside bond. 相似文献
7.
The reaction between nickel(II) nitrate and potassium phosphorus-1,1-dithiolates (di-sec-butyl and di-iso-butyl) in methanol yields 2:1 complexes which were characterized by FT-IR and NMR spectroscopy. 2:1 pyrazole adducts of both compounds were also obtained.The X-ray diffraction analysis of the compounds reveals square planar, four-coordination geometry for the homoleptic compounds and a six-coordinated distorted octahedral geometry for the adducts. In Ni[S2P(OBus)2]2 the molecules are associated through C-H?O hydrogen bonds (2.652 Å), and in Ni[S2P(OBui)2]2 the molecules are associated through C-H?S hydrogen bonds (2.948 Å). The pyrazole adducts are associated through N-H?O bonds and N-H?S bonds from the pyrazole nitrogen atoms, to form supramolecular assemblies. Thus, Ni[S2P(OBus)2(Pz)2]2 (Pz = pyrazole) forms bi-dimensional layers through N-H?O and N-H?S bonds (2.502 and 2.965 Å, respectively), whereas Ni[S2P(OBui)2(Pz)2]2 forms linear chains with N-H?S bonds 2.728 Å. The dithiophosphato groups behave as isobidentate chelating ligands. 相似文献
8.
Treatment of 6-Me-ApyH2 (6-methyl-2-amino-pyridine) with one equivalent of nBuLi followed by addition of 0.5 equivalents of Cl2SiMe2 unexpectedly yields the cyclodisilazane [(6-Me-Apy)2(μ-SiMe)2]. [(6-Me-Apy)2(μ-SiMe)2] was characterised by 1H, 13C and 29Si NMR and IR spectroscopy, elemental analysis and X-ray crystallographic methods. The X-ray structure reveals a dinuclear compound having a four-membered Si2N2 core with coplanar aromatic rings. 相似文献
9.
A new CoII/CoIII hexanuclear complex, [Co4IICo2III(dea)2(Hdea)4)(piv)4](ClO4)2·H2O 1, has been obtained by reacting cobalt(II) perchlorate, diethanolamine, and pivalic acid (H2dea = diethanolamine and piv = pivalato anion). The cobalt ions are held together by four μ3 and four μ2 alkoxo bridges as well as by four syn-syn carboxylato groups. The hexanuclear motif contains four Co(II) and two Co(III) ions. The {CoII4CoIII2(μ2-O)4(μ3-O)4} core can be described as a four face-sharing monovacant and bivacant distorted heterocubane units. The cobalt(III) ions are hexacoordinated. Two of the cobalt(II) are hexacoordinated, while the two others are pentacoordinated with a bipyramidal stereochemistry. The magnetic properties of 1 have been investigated in the temperature range 1.9-300 K. Compound 1 exhibits an overall antiferromagnetic behaviour with a ground singlet spin state. 相似文献
10.
In this paper it is reported the synthesis of the phosphonium salts [Ph2P(CH2)n(Ph)2PCH2COOMe]Br (n = 1 (1), 2 (2)) and [Ph2P(CH2COOMe)(CH2)n(Ph)2PCH2COOMe]Br2 (n = 3 (3)) derived from the reactions of the diphosphines dppm, dppe and dppp with methyl bromoacetate. By reaction of the monophosphonium salt of dppm and dppe with the strong base Na[N(SiMe3)2] the corresponding carbonyl stabilized ylides Ph2P(CH2)n(Ph)2PCHCOOMe (n = 1 (4), 2 (5)) were obtained. The Ph2P(CH2)2(Ph)2PCHCOOMe (5) ylide was reacted with Pd(II) and Pt(II) substrates. From these reactions were isolated exclusively complexes in which the ylide was chelated to the metal through the free phosphine group and the ylidic carbon atom. A further reaction of the Ph2P(CH2)2(Ph)2PCHCOOMe (5) ylide with 1.5 equiv. of Na[N(SiMe3)2] gives the bifunctionalized ketenylidene Ph2P(CH2)2(Ph)2PCCO (6) system. This cumulenic ylide reacts with Pt(II) complexes to form a chelated derivative in which IR and NMR spectra suggest the breaking of the CC bond of the -CCO group. 相似文献
11.
Reaction of NH4VO3 with 2,6-pyridinedimethanol in water at 85 °C followed by the room temperature addition of HCl (aq) yields [HVO2(pydim)]x (pydim = 2,6-pyridinedimethanolato dianion), as a sparingly soluble off-white solid. This acid may be deprotonated by titration with NaOH (aq), yielding Na[VO2(pydim)] · 4H2O, which has been structurally characterized by single-crystal X-ray diffraction. Treating Na[VO2(pydim)] · 4H2O with HCl (aq) regenerates [HVO2(pydim)]x, but reaction with additional NaOH (aq) displaces the pyridinedimethanolato ligand from the vanadium center. Similarly, treating [HVO2(pydim)]x with excess HCl (aq) strips the pyridinedimethanolato ligand from the vanadium center and yields the adduct [H3(pydim)]+Cl− as one component in a mixture of products. This adduct has been structurally characterized by single-crystal X-ray diffraction. The optimum pH range for stable dioxovanadium(V) complexes stabilized by the 2,6-pyridinedimethanolato ligand is at least 1.5-9.4. 相似文献
12.
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
13.
An investigation into the interactions between thiamine monophosphate (TMP) and anions has resulted in the preparation and X-ray characterization of the compounds (TMP)(Hg2Br5)·0.5H2O (1) and (TMP)2(Hg3I8) (2). In each compound the TMP molecule exists as a monovalent cation in the usual F conformation. The halogenomercurate anions occur in two-dimensional (2-D) network in 1 or one-dimensional (1-D) chain in 2. In both 1 and 2, the structures consist of alternating cationic sheets of the hydrogen-bonded TMP molecules and anionic sheets of the polymeric halogenomercurate anions. The TMP molecule binds to the polymeric anions through the characteristic ‘anion bridge I’, C(2)H?X?pyrimidinium (X=Br in 1 and I in 2), and electrostatic interactions between electropositive S(1) and halogen atoms. The ‘anion bridge II’ of the type N(4′1)H?X?thiazolium (X=phosphate group) plays a role in stabilizing the molecular conformation. The biological implication of the host-guest-like complexation between TMP and polymeric anions is discussed. 相似文献
14.
Elaine B. Vickers 《Inorganica chimica acta》2004,357(13):3889-3894
Magnetically ordered Ni[TCNE]2 · zCH2Cl2 (Tc = 13 K) is reported for the first time from the reaction of Ni(CO)4 with tetracyanoethylene (TCNE). A family of new solid solution room temperature magnets of VxNi1 − x[TCNE]y · zCH2Cl2 (0 ? x < 1; y ? 2) composition has been characterized by IR spectrometry, elemental analysis, and magnetic measurements (ac and dc susceptibility). Substitution of NiII for VII in V[TCNE]y · zCH2Cl2 does not alter the Tc significantly for x ? 0.05 and does not alter Hcr significantly for x > 0; however, the magnitude of M increases with x, as does the broadness of the peaks in the χ′(T) and χ″(T) ac susceptibilities. Hence, the magnetic properties of the room temperature V[TCNE]y · zCH2Cl2 magnet can be finely tuned via synthetic chemistry methodology, making this material more amenable in future technologies. 相似文献
15.
Infrared, far-infrared and Raman spectra of Re2(O2CCH3)4X2 (X = Cl, Br) and Re2(O2CCD3)4Cl2 have been recorded. Assignments of the vibrational spectra of Os2(O2CCH3)4Cl2 and its deuterated derivative have been completed together with the Re complexes on the basis of normal-coordinate analysis. Force constant calculation was made for the acetate ion as well as for a four-atomic unit (with the CH3 and CD3 groups considered as point masses) using optimized masses of 16.7, 17.8, 20.5 and 21.6 for 12CH3, 13CH3, 12CD3 and 13CD3 groups, respectively. The force constants of the acetate ion have been adopted to the starting force field of the M2(O2CCH3)4X2 type complexes. The metal-halide (0.889, 0.997 and 1.286 N cm−1) and metal-metal stretching (3.32, 3.34 and 3.57 N cm−1) force constants were obtained for Re2(O2CCH3)4Cl2Re2(O2CCH3)4Br2 and Os2(O2CCH3)4Cl2 complexes, respectively. It was shown that the so-called diatomic approximation in most cases overestimates the M-M stretching force constants by 30-40%. Much better correlation has been obtained to fit these force constants, which produced values very close to those obtained by full normal-coordinate calculations. The Re-Re stretching force constants showed a reasonable correlation with the Re-Re bond distances for 18 rhenium complexes. 相似文献
16.
Prashanth W. Menezes 《Inorganica chimica acta》2010,363(15):4299-7188
The isotypic layered transition metal borophosphates MII(H2O)2[B2P2O8(OH)2]·H2O (MII = Fe, Co, Ni) were prepared under hydrothermal conditions. Their crystal structures were determined by single-crystal X-ray diffraction data and revealed an isotypic relationship to Mg(H2O)2[B2P2O8(OH)2]·H2O, a structure containing wavy 63 nets formed by tetrahedral phosphate and hydrogenborate groups interconnected in an alternating fashion by sharing common apices. The crystalline compounds were also characterized by chemical analyses, scanning electron microscopy, energy dispersive X-ray analyses, thermal analyses, IR-spectroscopy and magnetic susceptibility measurements. 相似文献
17.
Carolina Alarcón-Payer Duane Choquesillo-Lazarte Guido Crisponi Juan Niclós-Gutiérrez 《Inorganica chimica acta》2005,358(6):1918-1926
Three new thiodiacetato-Cu(II) chelates have been synthesized and studied by X-ray crystallography and by thermal, spectral and magnetic methods. [Cu(tda)]n (1) is a 3D-polymer with a pentadentate tda, which acts with a fac-O2 + S(apical)-tridentate chelating conformation and as a twofold anti, syn-μ-η1:η1 carboxylate bridge. In its square pyramidal Cu(II) coordination (type 4 + 1) four O(carboxylate) donors define a close regular square base, but the Cu-S(apical) bond deviates 27.4° from the perpendicular to the mean basal plane. Each anti,syn-bridging carboxylate group exhibits two C-O (average 1.26(1) Å) and two Cu-O bonds (average 1.958(7) Å), which are very similar in length to each other. In contrast, the mixed-ligand complexes of [Cu(tda)(Him)2(H2O)] (compound 2, distorted octahedral, type 4 + 1 + 1) and [Cu(tda)(5Mphen)] · 2H2O (compound 3, distorted square pyramidal, type 4 + 1) have molecular structures and the tda ligand displays only a fac-O2 + S(apical)-tridentate conformation. The Cu-S(apical) bond lengths (2.570(1), 2.623(1) or 2.573(1) Å for 1, 2 or 3, respectively) are shorter than those previously reported for closely related Cu(II)-tda derivatives. The different tda ligand roles in their Cu(II) derivatives are rationalized on the basis of crystal packing forces driving in the absence or presence of auxiliary ligands (with two or three N-donor atoms). 相似文献
18.
David M.L. Goodgame Paul B. Hayman Richard T. Riley David J. Williams 《Inorganica chimica acta》1984,91(2):89-93
The preparations are reported of cis[Pt(caffeine)2Cl2]·0.4H2O, Pd(caffeine)2Cl2, the methanol adduct of the previously known compound K[Pt(caffeine)Cl3], and Pt(caffeine)(cytidine)Cl2. Crystals of [Pt(caffeine)2Cl2]·0.4H2O are tetragonal P42/n with a = 13.156(2) 0?, c = 12.734(2) 0?, Z = 4. The structure was refined on 945 reflections to R = 0.025. The molecule is cis with a crystallographic two-fold axis bisecting the ClPtCl and NPtN angles. The Pt is square planar with PtN and PtCl bonds of 2.029(5) Å and 2.271(2) Å respectively. There is a 5.4° dihedral angle between the imidazole and pyrimidine rings, and the imidazole ring is rotated away from the coordination plane by 86.4°. Symmetry related caffeine units pack parallel to each other with an inter-ring separation of 3.45 Å. 相似文献
19.
An oxalato-bridged binuclear iron(III) compound, Fe2(C2O4)Cl4(DMF)4 (DMF = dimethylformamide), was obtained by electrocrystallization for three weeks at 3.4 V and it displays a strong antiferromagnetic interaction of J = −6.74(4) cm−1. 相似文献
20.
Thomas E. Bitterwolf Wyatt Thornley Jenni L. Crawford 《Inorganica chimica acta》2008,361(11):3271-3282
Photolysis of cis-Fe(CO)4X2, where X = Br and I, results in low energy, facile rearrangement to the trans isomer with no evidence of CO-loss. In contrast, the isoelectronic cis-Mn(CO)4Br2 anion exhibits CO-loss upon photolysis with only weak evidence for the trans isomer. The photolysis of Mn(CO)5Br, Mn(CO)4Br(PBu3) and Mn(CO)3Br(PBu3)2 have also been examined in frozen matrices. 相似文献