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1.
Metallocene sulfides [Cp2M(μ-S)]2 (I, M  Zr4+; II, M  Hf4+ and Cp = cyclopentadienyl) have been synthesized. I and II show charge transfer absorption in the visible region. FT-Raman, Raman and IR spectra of these compounds are reported for the first time. The MS stretching bands have been assigned with the help of a pre-resonance effect. The approximate normal coordinate analysis of the coordination skeleton (D2h symmetry) aids the detailed assignment in the low frequency spectral region. Force constants of MCp and MS stretching imply that the bond order of HfL is higher than that of ZrL.  相似文献   

2.
Equilibrium geometries and force fields for the series of molecules (MeO)nSiMe4−n(I), (OH)nSiMe4−n(II), and (MeO)nSi(OH)4−n(III) with n = 1–4 are obtained at the DFT/B3LYP level of theory with 6-31G* and aug-cc-pVDZ basis sets in order to predict the structural parameters and vibrational spectra of these molecules, the larger part of which was not characterized experimentally. The performance of these theoretical methods was assessed on the existing spectral data for series I. The B3LYP/aug-cc-pVDZ method, firstly applied to this class of molecules, demonstrates a fair agreement with experimental vibrational frequencies even without empirical scaling. For molecules of series II and III vibrational spectra are predicted in order to supply spectral data for monitoring the sol–gel processes at the hydrolysis stage. The hyperconjugative strengthening of SiO bonds with the number of oxygen atoms coordinated to silicon leads to the growth of their frequencies, but the larger increase of νSiO (due to kinematic factors) occurs at the SiOMe/SiOH substitution. The predicted distinctive feature of series II and III is the appearance of bands with high IR intensity in the 1000–900 cm−1 spectral region that increase their frequencies with n. In series III it is accompanied with the steady increase of the νsSiO4 frequency in the 700–600 cm−1 range.  相似文献   

3.
This article presents the investigation results of polarized IR spectra of the hydrogen bond in N-methylacetamide (NMA) crystals measured in the frequency range of the proton and deuteron stretching vibration bands, νN–H and νN–D. A similar study was also performed for crystals of the deuterium isotopomers of the compound, D7-NMA (CD3CONDCD3) and D6-NMA (CD3CONHCD3). On the basis of the analysis of the linear dichroic and temperature effects, the two-branch structure of the νN–H bands in the spectra was ascribed to centrosymmetric hydrogen bond pairs in the lattice. Each hydrogen bond in such a dimeric system belonged to another chain of the associated molecules. The exciton interactions involving the dimer hydrogen bonds were considered to be responsible for the band shape generation. For the deuterium-bonded crystals the exciton interactions were found to be weaker since the νN–D bands were less split. Within an individual hydrogen or deuterium bond chain the in-chain exciton couplings involving hydrogen bonds were estimated as considerably weaker than the inter-chain ones. The exciton dilution retains the two-branch fine structure pattern of the “residualνN–H and νN–D bands. This means that the inter-chain couplings involving hydrogen bonds do not change, when the in-chain couplings vanish. These results are the evidence of the influence of non-conventional co-operative interactions occurring in the hydrogen bond systems on the spectra. These co-operative interactions are responsible for the non-random distribution of the hydrogen isotope atoms in the hydrogen bridge lattices, namely for the grouping of identical hydrogen isotope atoms in the dimers. The proposed interpretation of the IR spectra of the hydrogen bond in N-methylacetamide (NMA) crystals casts light on the spectra generation mechanisms and gives a new meaning to the traditional nomenclature applied for describing the νN–H band structure pattern in IR spectra of amides.  相似文献   

4.
FTIR spectra of the title carboxylic acids (IIII) with 4-substituents (H, CH3 or C6H5) and their related compounds IVVI with 4-(substituted phenyl) groups were measured in dilute CCl4 and CHCl3 solutions. The concentration dependence of FTIR spectra of IIV was also measured in these solutions. These spectra were subjected to curve analysis in order to quantitatively identify the rotational isomers of 3-carboxy group attributable to steric hindrance of the 4-substituents. For I, II and IIIVI, two, four and five ν(CO) bands were observed for their carboxy groups, respectively, indicative of monomer–dimer equilibrium and two and three kinds of rotational isomers for II and IIIVI, respectively. Compounds IIIVI were found to form intra-molecular hydrogen bonds between the trans-type of the 3-carboxy group and the π-electrons in the 4-benzene ring. We have worked out a method to estimate the association constant (K) of complicated monomer–dimer equilibria such as IIVI. The K values of IIV decrease remarkably in the order of H (I), C6H5 (III), CH3 (II) and C6H4-p-OCH3 (IV) in CCl4 and I, II, III and IV in CHCl3; these orders are discussed.  相似文献   

5.
Studies of IR and Raman spectra of monohydrates MI2[MIIICl5(H2O)] (where MI=K+, Rb+, Cs+ and MIII=Fe3+, In3+) at 1400-1900 cm−1 have been carried out. The medium intensity band, detected in the region 1580-1595 cm−1 was assigned to bending vibrations of water molecules (δHOH). The shift of the δHOH band towards low wavenumbers (1580-1595 cm−1) is a main sign of the water molecule interactions in the chain hydrates. Additionally in the IR and Raman spectra of these salts, the appearance of the low intensity band between 1750 and 1810 cm−1 (νx(H2O)) was observed. In the presented paper we also discuss the influence of MI and MIII cations on the position and splitting of these bands.  相似文献   

6.
Solutions of acetonitrile (I) in tetrachloromethane and deuteratred solvents (S) (benzene, acctonitrile, acetone and dimethylsulphoxide) have been studied by IR absorption spectra. The observed solvent effect on the IR spectrum of I was explained in terms of the existence of complexes with hydrogen bonding of the type NCCH3…solvent (S). The strength of the hydrogen bonding was characterized by enthalpies of specific interactions of I with solvents ΔHI/Sint(sp). The values ΔHI/Sint(sp) were determined both by IR spectroscopy and calorimetry and were found to be within the range 0.3–1.5 kcal mol−1.  相似文献   

7.
The complete assignment of the vibrational spectra of 2,5-dimethyl-2,4-hexadiene, 4-methyl-1,3-pentadiene and (E)-2-methyl-1,3-pentadiene was obtained from a comparative analysis of their i.r. and Raman spectra (solid, liquid and gas) in the range 3200-50 cm−1. It is shown that particular vibrational motions strongly interact to give rise to very characteristic modes depending on the site of methyl substitution. The comparison of our results with those of analogous shorter and larger polyenes and polyenals allows us to discuss the various local coupled motions characteristic of unsubstituted (CHCH CH)CH and methyl substituted (CHC(CH3)CH), ((CH3)2CCH) or (CH3CHCH) fragments in polyenic chains.  相似文献   

8.
Polarized Raman spectra measured in the temperature range between 10–293K are reported for SFDH, SFDD single crystals and isotopically samples of Sr(HCOO)2.2(H,D)2O.AtT=293 K the uncoupled OD(H) stretching motions are observed in the range ν=2200–2600(3000–3500) cm−1 Plausible assignments to the distinct crystallographically non equivalent H2O(D2O) molecular group are given. The investigation has been conducted to elucidate this situation as well as that the structural role of lattice water molecules in molecular crystals.  相似文献   

9.
Cluster bond enthalpies, EL(BB), and orders, n?(BB), for the structurally characterised closo anions, BnHn2? (n = 6 and 8–12), have been estimated using the logarithmic length—enthalpy and enthalpy—order relationships EL(BB) (kJ mol?1) = 1.766 × 1011 [L(BB)]?4.0 and EL(BB) (kJ mol?1) = 318.8[n?(BB)]0.697, respectively. In a parallel study, the molecular-orbital bond index CNDO-based calculation method has been used to give BB and BH bond indices, I(BB) and I(BH), from which bond index based bond enthalpies, EI, have been calculated using the relationships EI(BB) = 297.9 I(BB) and EI(BH) = 374.8I(BH) (enthalpies in kJ mol?1; lengths in pm). From these, total skeletal bond enthalpies Σ E(BB), and total bond enthalpies, Σ E(BB) + Σ E(BH), have been calculated. Although calculated values of EL and Σ EL generally exceed those of EI and Σ EI by some 8% and calculated values of I generally exceed those of n? by a greater amount, the trends in these parameters for the series of BnHn2? anions are very similar, showing the greater efficiency with which the n + 1 skeletal electron pairs are used as n increases. However, the two approaches differ in that, whereas the Σ EI values suggest that the anions are all of comparable stability, the ΣEL values clearly show B6H62?, B10H102? and B12H122? to be more stable than B8H82?, B9H92? and B11H112?. The interatomic distances in B7H72? and in the unknown B5 H52? are estimated and used to assess their relative stabilities. The EL values suggest that B7 H72? is of comparable stability to B8H82? etc., but show B5H52? as relatively unstable. The EI values suggest that both of these anions should be relatively stable members of the series of closo anions.  相似文献   

10.
The treatment of the hexacarbonylmetal compounds M(CO)6 (M = Cr. Mo, W) with two equivalents Me3PCH2 yields the phosphonium acylmetalphosphorus ylides Me4P[(CO)5MC(O)CHPMe3] 1a–1c. Their reaction with Me3SiOSO2CF3 leads via O-silylation to formation of the neutral “siloxy(ylidecarbene) complexes” (CO)5MC(OSiMe3)CHPMe32a–2c, which are protonated by HX (X = Cl, CF3SO3) to give the thermolabile carbene complexes [(CO)5MC(OSiMe3)H2CPMe3]X, 3a, 3b. 1H, 13C NMR and IR data suggest, that delocalization of the ylidic charge to the carbene carbon generates a metal-coordinated vinyl group in the case of 2a–2c. In addition this fact is proved by the X-ray analysis of 2c, for which a C(ylide)C(carbene) bond distance of 133 pm is found. 2a–2c are obtained as pure E-isomers but can be converted to the Z-isomers 2a′–2c′ upon photolysis.  相似文献   

11.
Three new copper coordination polymers [Cu(L) · 6H2O] n (I), [Cu2(L)2] n (II), and [Cu(HL)2] n (III), where H2L is N-[(3-pyridine)-sulfonyl]aspartate, have been synthesized and characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1435871 (I), 1435872 (II), 1435873 III), elemental analysis and IR spectra. Moreover, the variable-temperature magnetic susceptibility had been studied for complex I. A structural comparison of these polymers suggests that different reaction temperatures play important role in the construction of resulting architectures for IIII.  相似文献   

12.
Isomeric pairs of silicon-germanium compounds containing a SiGe bond (Me3SiGePh3 (I) and Ph3SiGeMe3 (II); FpSiMe2GeMe3 (III) and FpGeMe2SiMe3 (IV) (Fp = (η5-C5H5)Fe(CO)2); IFpSiMe2GeMe3 (V) and IFpGeMe2SiMe3 (VI) (IFp = (η5-C9H7)Fe(CO)2); IFpSiMe2GePh3 (VII) and IFpGeMe2SiPh3 (VIII) and the complex FcSiMe2GeMe2Fc (IX) (Fc = ferrocenyl) have been synthesized and examined by mass spectrometry.The R3SiGeR′3 compounds I and II exhibit considerable exchange of R groups to produce [R3-nR′nSi]+ and [R′3-nRnGe]+ ion in progressively lesser amounts as n = 1 → 2 → 3. For the metal-substituted complexes containing the grouping FeSiGe fragmentation occurs predominantly via SiGe bond cleavage with formation of ions containing the silylene ligand [FeSiR2]+. Complexes with the FeGeSi backbone undergo preferential scission of the FeGe bond, illustrating the general bond strength trend FeSi > SiGe. Upon direct cleavage of the SiGe bond in R3SiGeR3 compounds, the percentage of the charge carried by [R3Si]+ ions significantly exceeds that carried by [R3Ge]+ ions, reflecting the greater electronegativity of Ge polarizing the SiGe bond.  相似文献   

13.
《Vibrational Spectroscopy》2010,52(2):218-225
Plausible structures of the titanium tetramethoxide trimer were optimized at the B3LYP/6-31+G* level. From the four types of structures of the Ti3O12 cage found earlier for the Ti(OH)4 trimer only two isomers were found as energy minima on the Ti3(OMe)12 potential energy surface. One isomer (I), belonging to the Ci point group, is built from three interconnected titanium oxide tetrahedra with a linear arrangement of titanium atoms. This structure have a titanium oxide skeleton similar to that of Ti3(OH)12. The other isomer (II), of C2 symmetry, is built by edge sharing TiO6 groups. Theoretical IR spectra of these isomers are compared with reported experimental IR spectra of solid titanium tetramethoxide and newly obtained Raman spectra of commercial powders. It was shown that the number and position of observed bands in the CO stretching region of the IR spectra of the so-called modification A of solid titanium tetramethoxide are in a good agreement with the predicted vibrational spectrum of trimer I. The equilibrium structure and IR and Raman spectra were also obtained for the Ti4(OMe)16 tetramer. The comparison of the predicted vibrational spectrum with the experimental IR spectra of modification B as well as of the Raman spectrum of solid titanium tetramethoxide allows us to confirm the tetrameric structure of this modification and to propose the similar structure for commercial samples.  相似文献   

14.
The Raman spectra of aqueous and solid sodium dithionite have been recorded. Differences in the location, intensity, and number of observed bands are attributed to conformational changes in the dithionite ion. The structure of the aqueous ion is non-planar with a C2h symmetry with an SS bond distance estimated to be 0.220–0.226 nm, as opposed to the dithionite structure in the Na2S2O4·2H2O salt which is known to have C2ν structure with a bond distance of 0.2389 nm. The Raman spectra of aqueous dithionite are assigned to Ag (SO) = 997 cm?1; Bg (SO) at 912 cm?1, Bg SO2 twist at 324 cm?1. The remaining bands are a strong Ag, the SO2 wag, the SO2 scissor, and the SS stretch at 584, 461, and 232 cm?1, respectively, but due to coupling all three motions are expected to exhibit substantial SS character. The variation of the spectra of the solid and aqueous sodium dithionite indicate strong environmental effect on the structure of the anion.  相似文献   

15.
In this paper, the results of a comparative study of a salt-like paramagnetic Mn(II) (d 5) complex [MnII(1,10-C12H8N2)3]2+[CoIII(B9C2H11)2] 2 (I) against [MnII(1,10-C12H8N2)2(NCS)2]0 (II) and [MnII(1,10-C12H8N2)3]2+[B9C2H12] 2 (III) are presented. Complexes I and III were synthesized by precipitating the Mn(II) cations with the corresponding anions in the stoichiometric ratio at a pH of ~ 4.5 and were studied by X-ray diffraction analysis on single crystals; by IR, Raman, and EPR spectroscopy; and using magnetochemical methods. The structures and crystal-chemical parameters of I at 190 and 293 K are identical. The crystals are mono-clinic; space group P21/n. Two crystallographic types of the [Co(B9C2H11)2] anion in structure I have different conformational combinations (cisoid and transoid) of the –C2– groups in each pair of the B9C2H2– 11 cluster ligands. The short contacts C–Hδ+···δ–H–B between different-type hydrogen atoms show themselves in the IR spectra. The apparent magnetic moments of the Mn(II) atom in I, II, and III at 293 K correspond to μ = 5.86 μB and do not depend on its ligand or anion environment. The temperature dependences μ = f(T) pass through a maximum at about 20 K, which suggests the occurrence of ferromagnetic exchange interactions in complexes I and III, which both contain cluster carborane derivatives with three-dimensional aromaticity.  相似文献   

16.
New germanates Pb2MIII2Ge2O9 (MIII = Fe, Mn, Sc, In) and silicates Pb2MIIMIVSi2O9 (MII = Mg, Ni, Co, Cu for MIV = Sn; MII = Co, Ni for MIV = Ti) have been synthesized by solid state reaction. Their X-ray powder diagrams may be indexed in the orthorhombic system and show that these compounds are isostructural with kentrolite Pb2Mn2Si2O9. Doubts are expressed about the published structure of kentrolite and it is shown that some aspects of the structure should be re-examined.The I.R. and Raman spectra of these compounds are fairly complicated, and their discussion is restricted to the region of SiO or GeO stretching frequencies. These spectra show the existence of a pyro-silicate or -germanate group. The symmetric and antisymmetric frequencies of the SiOSi bridge have been identified with the help of 28Si30Si isotopic shifts. Their difference νas?νsym depends on the ionic radius of the cations, and points to a non-linear bridge of the pyrosilicate group.  相似文献   

17.
Three new complexes, namely {[Ln(L)3(2,2′-Bipy)] n · H2O} (Ln = Pr (I), Sm (II), and Nd (III)) (HL = 3-(2-hydroxyphenyl)propanoic acid), have been synthesized and structurally characterized. The structural determinations indicated (CIF files CCDC nos. 1472729 (I), 1472730 (II), 1472734 (III)) that IIII have similar dinuclear structures, which can be further linked into 2D sheet via the hydrogen bond interactions. Furthermore, the luminescent properties of IIII show the strong emissive power and feature.  相似文献   

18.
The infrared carbonyl stretching (νCO) frequencies as well as the carbon—iodine (νCI) Raman and infrared frequencies for some ω-iodo-p-substituted acetophenones are reported. Although in the title compounds the solvent effect on the carbonyl band does not indicate the existence of cis/gauche rotational isomerism, the comparison between the νCO frequencies in the fundamental transition with those in the 1st overtone (in CCl4) indicates the presence of the cis/gauche rotational isomerism. On going from electron-donating to electron-attracting substituents in the ω-iodo-series, the progressive increase in the gauche carbonyl shifts (Δνg) together with the progressive decrease in the νCI frequencies suggest the increasing contribution of the hyperconjugative interaction between πCO and σCI orbitals. The u.v. spectra of the title compounds display the n → π*CO band which is bathochromically shifted in relation to the corresponding acetophenones, indicating the π*CO/σ*CI hyperconjugative interaction in the excited state. [13C] NMR data for the methylene group of the ω-iodoacetophenones in comparison with those of ω-bromoacetophenones [1] as well as with those for the methyl group of the unsubstituted acetophenones corroborates the existence of the πCOCI hyperconjugation in the fundamental state of the title compounds.  相似文献   

19.
This article summarizes and presents the obtainable characteristic IR spectra of the existing heterothiometallic cluster compounds containing the [MXS3]2− (X=O, S; M=V, Mo, W, Re) moiety. The MS stretching vibration modes are classified into four categories including ν(MSt), ν(Mμ2-S), ν(Mμ3-S) and ν(Mμ4-S) according to the different conjunction ways between the transition metal and sulfur atoms. The structures of the heterothiometallic cluster compounds could be inferred from their characteristic IR spectra, the core structure's symmetry of the heterothiometallic clusters and the M/M′ ratio.  相似文献   

20.
This paper presents the investigation results of the polarized IR spectra of 3-hydroxybenzaldehyde and 4-hydroxybenzaldehyde crystals measured at 293 and 77 K. Analysis of the results concerned the linear dichroic, H/D isotopic and temperature effects observed in the spectra of the hydrogen and deuterium bond at the frequency ranges of the νO–H and the νO–D bands, respectively. The main spectral properties of the crystals were interpreted in terms of the “strong-coupling” theory on the basis of the hydrogen bond dimer model. The spectra revealed that the strongest vibrational exciton coupling involved the closely-spaced hydrogen bonds, each belonging to a different chain of associated molecules. The reason for two different crystalline systems, are characterized by almost identical νO–H and νO–D band shapes, is explained. It was proved that a random distribution of the protons and deuterons took place in the lattices of the isotopically diluted crystals.  相似文献   

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