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1.
《Chemical physics letters》2003,367(1-2):245-251
The electronic structures and energies of (H2O)n·CCH and (H2O)n·HCC complexes (n=1–3) between CCH and water have been theoretically investigated at the UB3LYP/6-311++G(2df,p)//UB3LYP/6-311G(d,p) level. The complexes with n=2–3 are cyclic structures with homodromic hydrogen-bond chain. The (H2O)n·CCH (n=1–3) complexes show increasing stabilities towards CCH- or H2O-eliminations of 2.3, 5.8 and 7.6 kcal/mol and are energetically more stable than the corresponding (H2O)n·HCC complexes by 0.8, 2.7 and 3.4 kcal/mol, respectively, due to the charge-separation-enhanced hydrogen bonds within (H2O)n·CCH (n=2,3). Strong interactions between CCH and (H2O)2 and (H2O)3 clusters suggest special solvent effects of water on the chemical behavior of unsaturated radicals.  相似文献   

2.
We have assessed the ability of 52 methods including 15 multicoefficient correlation methods (MCCMs), two complete basis set (CBS) methods, second-order M?ller-Plesset perturbation theory (MP2) with 5 basis sets, the popular B3LYP hybrid functional with 6 basis sets, and 24 combinations of local density functional and basis set to accurately reproduce reaction energies obtained at the Weizmann-1 level of theory for hydronium, hydroxide, and pure water clusters. The three best methods overall are BMC-CCSD, G3SX(MP3), and M06-L/aug-cc-pVTZ. If only microsolvated ion data is included, M06-L/aug-cc-pVTZ is the best method; it has errors only half as large as the other density functionals. The deviations between the three best performing methods are larger for the larger hydronium- and hydroxide-containing clusters, despite a decrease in the average reaction energy, making it impossible to determine which of the three methods is overall the best, so they might be ranked in order of increasing cost, with BMC-CCSD least expensive, followed by M06-L/aug-cc-pVTZ. However, the cost for M06-L will increase more slowly as cluster size increases. This study shows that the M06-L functional is very promising for condensed-phase simulations of the transport of hydronium and hydroxide ions in aqueous solution.  相似文献   

3.
The complexes [Cd(H2O)6](C5HN2O6)2 · 2H2O (I) and [Co(H2O)6](C5HN2O6)2 · 2H2O (II) were obtained in the crystalline state by reactions of cobalt chloride and cadmium chloride with ammonium 4-nitro-2,3,5,6-tetraoxopyridinate, (NH4)2 · (C5HO6N2)2. Their cocrystallization gave the heterometallic complex [Cd0.32Co0.68(H2O)6](C5HN2O6)2 · 2H2O (III). The crystal and molecular structures of complexes I-III were determined by X-ray diffraction. It was demonstrated that the complexation reactions occur by replacement of two ammonium cations 4-nitro-2,3,5,6-tetraoxopyridinate by the complex cations [M(H2O)6]2+. The tetraoxopyridinate anions and the complex cations are hydrogen-bonded through the coordinated and crystallization water molecules as well as through the O atoms of the organic anion. The thermolysis of complexes I and II was examined by TGA.  相似文献   

4.
Summary. Two novel compounds, [Co(phen)3]2V4O12·phen·22H2O (1) and [Ni(phen)3]2 V4O12·phen·22H2O (2), were prepared from KVO3–1,10-phenanthroline (phen)–Co(NO3)2, resp. NiCl2–H2O reaction systems. The compounds 1 and 2 are isomorphous and crystallize in triclinic system, space group P-1. Their crystal structures are formed by two types of layers parallel to 001: a cationic one consisting of [MII(phen)3]2+ ions and an anionic one containing the cyclic V4O12 4– anions. The solvate phenanthroline and crystal water molecules are located in the cationic and anionic layers, respectively. The IR spectra of 1 and 2 are consistent with the presence of the cyclic V4O12 4– anions in the complexes.Received November 13, 2002; accepted (revised) February 3, 2003 Published online June 2, 2003  相似文献   

5.
Two novel examples of sandwich type heteropolyanions were synthesized and characterized by X-ray crystal structure and elemental analysis as well as infrared spectroscopy. Na13[H3Cu4(H2O)2(CuW9O34)2]39H2O (1) and Na9K[Fe4(H2O)2(FeW9O34)2]32H2O (2) were prepared in aqueous solution by reaction of sodium tungstate with FeIII and CuII cations, respectively. 1 crystallizes in the monoclinic space group P21/n (a=13.054(3) Å, b=17.729(4) Å, c=20.998(4) Å, =93.50(3)°), while 2 is triclinic, space group P¯1 (a=12.316(2) Å, b=13.716(3) Å, c=14.925(3) Å, =99.36(3)°, =104.21(3)°, =101.55(3)°). Each anion consists of two [XW9O34] n moieties (X=FeIII, n=11 (1) and CuII, n=12 (2)) which can be described as -B-isomers of the defect Keggin anion. These units are linked via a belt of four FeIIIO6 or CuIIO6 groups. Two transition metal atoms fill their octahedral coordination sphere with one additional water ligand.  相似文献   

6.
Compounds p-HOOCC6F4COOH · H2O (H2L · H2O), [Tb2(H2O)4(L)3 · 2H2O] n (I), and Tb2(Phen)2(L)3 · 2H2O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H2L · H2O is built of centrosymmetric molecules H2L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb2(H2O)4(L)3] n and molecules of water of crystallization. The ligands are the L2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO9 is a distorted three-capped trigonal prism. Acid H2L manifests photoluminescence in the UV region (??max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb3+ ions, and the band with ??max = 545 nm (transition 5 D 4?? 7 F 5) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.  相似文献   

7.
Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.  相似文献   

8.
The complexes [M(H2O)5][Cu(pdc)2]·2H2O [M=Ni(II) 1, Co(II) 2, Mn(II) 3; pcd=2,6-pyridinedicarboxylato] are prepared and their crystal structures, magnetic susceptibilities and UV-Visible properties reported. In all cases, the Cu(II) ion occupies the chelating site in the pdc ligand, while the M(II) occurs as a pentaaqua ion bridged to the [Cu(pdc)2] moiety through a carboxylate as demonstrated by both UV-Visible spectroscopy and X-ray diffraction. Single crystal X-ray diffraction shows the three complexes to be isostructural. Weak antiferromagnetic interactions between the metal ions are observed in 1 and 3, while the magnetic behavior of 2 is dominated by single ion anisotropy.  相似文献   

9.
Heterometallic compounds of general formula [Fe 2 III MIIO(O2CR)6(H2O)3] · 3H2O (R = CH3, M = Co, Ni; R = CCl3, M = Co, Ni) have been studied by XPS. The compounds have been identified as high-spin complexes with metal atoms in oxidation states M(II) and M(III). Analysis of the XPS data revealed the tendency of the XPS pattern and magnetic parameters of molecules to change with a change in the electronic nature of metal atoms. The assignment is based on the degree of covalence of the M-O bond. In chloro-substituted heterocomplexes, electron density delocalization on the metal atoms with metal-to-ligand charge transfer through three bonds (M-O-C-C) is observed. The substitution in terminal groups leads to the change in the electron density distribution between the carboxylate and terminal groups.  相似文献   

10.
11.
Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...  相似文献   

12.
A polymeric malonato-bridged copper(II) complex, {[Cu(H2O)3][Cu(MAL)2]· 2H2O}, and a mononuclear malonato-copper(II) complex with triethanolamine, [Cu(MAL)(TEA)]·H2O, have been prepared and characterized by elemental analyses, i.r., u.v.–vis, magnetic measurements and single crystal X-ray diffraction. The polymeric complex consists of one-dimensional chains containing the MAL bridged [Cu(H2O)3]2+ and [Cu(MAL)2]2– ions and each MAL ligand simultaneously exhibits chelating bidentate (at one copper atom) and bridging (at the adjacent copper atom) coordination modes. The intrachain Cu1...Cu2 separation is 4.963 Å and the polymeric complex exhibits antiferromagnetic behaviour. In the mononuclear complex, the copper(II) ion is octahedrally coordinated by one bidentate MAL and one tetradentate neutral TEA ligands. The i.r. spectra and thermal decompositions of both complexes are described.  相似文献   

13.
X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH3)6](MoO4)Cl·3H2O and [M(NH3)6](ReO4)3·2H2O (M = Ru, Ir) complex salts. The features of the fragment packing are studied.  相似文献   

14.
Five optimized geometries of F-·(H2O)n (n = 1, 2) were obtained with ab initio calculation at the B3LYP/6-311++G** level.The accurate intermonomer interaction energy was calculated using the MP2 electron correlation correction as well as the basis set superposition error correction by the Boys-Bernardi "counterpoise" protocol.Natural bond orbital (NBO) theory was applied to quantify the relative strength of these interactions and account for their effects on the stability, structural and vibrational parameters of Fˉ·(H2O)n (n = 1, 2).It is shown that the charge transferring from the lone pair of F-1 to the σ*OH(…F) antibonding orbital is important.The results indicate the occupancy of σ*OH(…F) is increased (denoted Δσ*OH(…F)) and the ΔROH(…F) bond is leng- thened (denoted (ROH(…F)), leading to the red-shift and the red-shift values have linear correlation with both Δσ*OH(…F) and ΔROH(…F).  相似文献   

15.
A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc=5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a=9.599(3), b=18.699(5), c=7.557(2) (A), β= 108.198(4)°, V=1288.6(6) (A)3, Z=4, Mr=382.60, Dc=1.972 g/cm3, F(000)=760, μ=1.740, the final R=0.0555 and wR=0.0995 for 1732 observed reflections with Ⅰ > 2σ(Ⅰ). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework.  相似文献   

16.
For the d(0) complex [{Zr(CpSiMe(2)H)Cl(3)}(2)] which contains a linear Si-H···Zr interaction across the dimer, DFT calculations are in good agreement with X-ray structures. The BP86 functional shows a slightly stronger interaction than B3LYP but for qualitative purposes either functional is sufficient. QTAIM analysis shows a bond critical point (bcp) for the interaction, a small negative value for the total energy density [H((r))] and the H atomic basin decreases in energy, E(H), and atomic volume compared to the free ligand. NBO analysis showed E(2) for Si-H σ to Zr(dz(2)) donation at 42.8 kcal mol(-1) and a 34% spatial overlap for the interaction consistent with an inverse hydrogen bond. The Wiberg bond index for the interaction is 0.1735 (0.7205 for the Si-H bond), ν((Si-H)) and (1)J((Si-H)) at 2060 cm(-1) and 145.4 Hz compared to 2183 cm(-1) and 172.1 Hz in the free ligand. Using a "synthesis by computation" approach to forming like complexes, similar features were found for [{Hf(CpSiMe(2)H)Cl(3)}(2)]. The titanium complex [{Ti(CpSiMe(2)H)Cl(3)}(2)] does not contain any Si-H···Ti interaction as rotation about the C-Si bond of the ligand occurs to place the Si-H bond hydrogen closer to a terminal chloro ligand across the dimer. An increase in electron density on the metal in the d(2) complex [{Mo(CpSiMe(2)H)Cl(3)}(2)] results in a stronger interaction with a distinct QTAIM analysis bcp [ρ((r)) 0.0448 a.u.], a small negative value for H((r)) and a much reduced H atomic volume. NBO analysis shows E(2) for Si-H σ to Mo(dz(2)) donation at 143.1 kcal mol(-1) and a 29% spatial overlap. Mo(dz(2)) to Si-H σ* donation (back donation) is minimal [E(2) 1.3 kcal mol(-1), ~1% spatial overlap]. The Wiberg bond index is 0.3114 (0.5667 for the Si-H bond), ν((Si-H)) 2015 cm(-1) and (1)J((Si-H)) 120.6 Hz.  相似文献   

17.
《Solid State Sciences》2000,2(6):607-614
We have investigated the crystal structures of CsLnFe(CN)6·nH2O (Ln=lanthanide, n=4,5), as well as TlTmRu(CN)6·3H2O. These phases can be thought of as derivatives of LnFe(CN)6·4H2O, where, simultaneously, an alkali ion (or Tl+) is introduced while the valence of Fe is reduced from Fe3+ to Fe2+. A new arrangement of the structural units is observed in the CsLnFe(CN)6·5H2O, where the coordination of the Ln-ion is changed to a bisdisphenoid. The resulting LnN5O3 units alternate with Fe(CN)6 units to form an overall rocksalt-type ralted lattice that accommodates the alkali ions in interstitial sites. Due to the arrangement of the water molecules, a layer structure results.  相似文献   

18.
Fourteen bis(citrato)germanates(IV) and bis(citrato)stannates(IV) were prepared, in particular, [M(H2O)6][Ge(HCit)2] · 4H2O (M = Mg (I), Mn (II), Fe (III), Co (IV), Ni (V), Cu (VI), Zn (VII)) and [M(H2O)6][Sn(HCit)2] · nH2O (M = Mg, n = 4 (VIII); Mn, n = 2 (IX); Fe, n = 4 (X); Co, n = 4 (XI); Ni, n = 4 (XII); Cu, n = 4 (XIII); Zn, n = 3 (XIV)) (H4Cit is citric acid). The purity and the composition of the products were determined by a set of physicochemical methods including elemental analysis, thermogravimetry, and IR spectroscopy. The structures of I, II, IV, VI, VII, VIII, XI, and XII were determined by X-ray diffractometry. All eight crystals composed of centrosymmetrical octahederal [M(H2O)6]2+ cations, [Ge(HCit)2]2? (or [Sn(HCit)2]2?) anions, and crystal water molecules are isostructural. The structural units in I, II, IV, VI, VII, VIII, XI, and XII are connected by systems of hydrogen bonds to form a three-dimensional framework.  相似文献   

19.
Two new supramolecular compounds [M(4,4′-bipy)2 (H2O)4] ·?(4,4′-bipy)2 ·?(3,5-daba)2 ·?8H2O (M=Zn(1) or Mn(2), 4,4′-bipy =?4,4′-bipyridine, 3,5-daba =?3,5-diaminobenzoic acid anion) were synthesized and characterized by elemental analysis and X-ray crystal diffraction. In [M(4,4′-bipy)2(H2O)4]2+, the M(II) is coordinated by two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four waters to form an octahedral configuration. There exist uncoordinated 4,4′-bipy molecules, 3,5-diaminobenzolate counterions and water guests in the compounds. The 3D structures of the title supramolecular compounds are constructed by rich hydrogen bonds among [M(4,4′-bipy)2(H2O)4]2+, uncoordinated 4,4′-bipy molecules, water molecules and 3,5-daba, containing a diverting hexa-member water ring.  相似文献   

20.
By reacting the K, Rb, Cs, or Tl carbonates with excess phosphoric acid, crystals of superacid phosphites, namely, (RbH2PO3)2· H3PO3(I), (TlH2PO3)2· H3PO3(II), KH2PO3· H3PO3(III), -CsH2PO3· H3PO3(IV), and -CsH2PO3· H3PO3(V), were synthesized. Their structures were determined by single-crystal X-ray diffraction analysis at 150 K. Crystals I: triclinic system, space group , a= 7.713(2) Å, b= 8.679(3) Å, c= 9.235(3) Å, = 79.36(3)°, = 67.60(2)°, = 88.13(3)°, R 1= 0.0252; crystals II: triclinic system, space group , a= 7.690(3) Å, b= 8.494(3) Å, c= 9.292(4) Å, = 79.48(3)°, = 66.72(3)°, = 85.45(3)°, R 1= 0.0485; crystals III: monoclinic system, space group P21/c, a= 8.726(3) Å, b= 12.182(4) Å, c= 6.354(2) Å, = 104.14(3)°, R 1= 0.0241; crystals IV: orthorhombic system, space group P212121, a= 6.033(1) Å, b= 6.444(1) Å, c= 18.345(4) Å, R 1= 0.0172; crystals Vare monoclinic, space group C2/c, a= 9.990(3) Å, b= 12.197(4) Å, c= 6.866(2) Å. = 118.14(3)°, R 1= 0.0181. The hydrogen bonding systems form corrugated bands (Iand II), bent layers (III), individual tubes with rectangular cross sections (V), or a three-dimensional framework (IV). A comparative analysis of the crystal structures of acid phosphites with different compositions was performed.  相似文献   

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