Indirect adsorbate-adsorbate interactions mediated through the surface electronic structure of the Si(100) surface

Indirect adsorbate-adsorbate interactions between adsorbed ammonia (NH3) molecules on the Si(100) surface are investigated using density functional theory. Two different nonlocal effects mediated through the surface electronic structure are observed: "poisoning" and hydrogen bonding. We find that adsorbed NH3 "poisons" adsorption of NH3 on neighboring Si dimers on the same side of the dimer row whereas neighboring NH2(a) groups favor this configuration. Adsorption of NH3 involves charge transfer to the surface that localizes on neighboring Si dimer atoms, preventing adsorption of NH3 at these sites. These indirect interactions are similar to Friedel-type interactions observed on metal surfaces with an estimated range of less than 7.8 A on the Si(100) surface. These interactions may be manipulated to construct local ordering of the adsorbates on the surface.     

Physisorption of N2, O2, and CO on fully oxidized TiO2(110)

Physisorption of N(2), O(2), and CO was studied on fully oxidized TiO(2)(110) using beam reflection and temperature-programmed desorption (TPD) techniques. Sticking coefficients for all three molecules are nearly equal (0.75 +/- 0.05) and approximately independent of coverage suggesting that adsorption occurs via a precursor-mediated mechanism. Excluding multilayer coverages, the TPD spectra for all three adsorbates exhibit three distinct coverage regimes that can be interpreted in accord with previous theoretical studies of N(2) adsorption. At low coverages (0-0.5 N(2)/Ti(4+)), N(2) molecules bind head-on to five-coordinated Ti(4+) ions. The adsorption occurs preferentially on the Ti(4+) sites that do not have neighboring adsorbates. This arrangement minimizes the repulsive interactions between the adsorbed molecules along the Ti(4+) rows resulting in a relatively small shift of the TPD peak (105 --> 90 K) with increasing coverage. At higher N(2) coverages (0.5-1.0 N(2)/Ti(4+)) the nearest-neighbor Ti(4+) sites become occupied. The close proximity of the adsorbates results in strong repulsion thus giving rise to a significant shift of the TPD leading edges (90 --> 45 K) with increasing coverage. For N(2)/Ti(4+) > 1, an additional low-temperature peak (approximately 43 K) is present and is ascribed to N(2) adsorption on bridge-bonded oxygen rows. The results for O(2) and CO are qualitatively similar. The repulsive adsorbate-adsorbate interactions are largest for CO, most likely due to alignment of CO dipole moments. The coverage-dependent binding energies of O(2), N(2), and CO are determined by inverting TPD profiles.     

Determination of the constants of affinity of FeCl3, CuCl2, and ZnCl2 for a nitrogen-containing organosilane bonded on Al2O3-cellulose acetate hybrid material surface from ethanol solution

This work describes the preparation and characterization of a cellulose acetate fiber coated with Al(2)O(3), resulting in the organic-inorganic hybrid Cel/Al(2)O(3). Furthermore, the hybrid was modified by attaching organofunctional groups by reaction with the precursor reagents (RO)(3)Si(CH(2))(3)L (L=NH(2), NH(CH(2))(2)NH(2), NH(CH(2))(2)NH(CH(2))(2)NH(2), and N(2)C(3)H(3) (imidazole)), resulting in Cel/Al(2)O(3)/Si(CH(2))(3)NH(2) (1), Cel/Al(2)O(3)/Si(CH(2))(3)NH(CH(2))(2)NH(2) (2), Cel/Al(2)O(3)/Si(CH(2))(3)NH(CH(2))(2)NH(CH(2))(2)NH(2) (3), and Cel/Al(2)O(3)/Si(CH(2))(3)N(2)C(3)H(3) (4). The amounts of attached organofunctional groups were (in mmol per gram of the material) 1=1.90, 2=1.89, 3=1.66, and 4=1.35. The isotherms of adsorption of FeCl(3), CuCl(2), and ZnCl(2) by Cel/Al(2)O(3)/Si(CH(2))(3)L from ethanol solutions were obtained at 298 K. Accurate estimates of the specific sorption capacities and the heteregeneous stability constants of the immobilized metal complexes were determined with the aid of several computational procedures. It is shown that the sorptional capacities are much less than the concentrations of the attached organofunctional groups. As all sorption isotherms are fitted properly with the Langmuir isotherm equation, the effects of the energetic heterogeneity and the lateral interactions do not affect the chemisorption equilibria. The heterogeneous stability constants of the immobilized complexes are fairly high, which provides efficient removal of the metal ions from solutions by the hybrid materials.     

Adsorption study of alkyl-silicas and methylsiloxy-silicas.

We report the synthesis and adsorption study of the lyophobic porous silicas. Four adsorbents were prepared and tested: (1) octyl-silica, (2) hexadecyl-silica, (3) bis(trimethylsiloxy)-silica, and (4) oligo(dimethylsiloxane)-silica. Octyl- and hexadecyl-silicas were prepared via the reaction of silica with (CH3)2NSi(CH3)2CnH(2n+1) (n=8 and 16), the reactions were carried under the optimized conditions yielding high bonding densities of alkyl groups approximately 2.9-3.0 groups/nm2 and highly uniform non-polar adsorbents. Bis(trimethylsiloxy)-silica was prepared via the reaction silica with ClSi(CH3)2(CH2)10Si(CH3)[OSi(CH3)3]2. Oligo(dimethylsiloxane)-silica was prepared via the reaction of silica with ClSi(CH3)2-[OSi(CH3)2]2-Cl. Adsorption of small organic compounds (n-alkanes, alkylbenzene, benzene, diethyl ether) was investigated using two methods, classical static adsorption and gas chromatography. Thermodynamic parameters (heat, Gibbs energy, and entropy) of the adsorption of organic compounds were studied as a function of the nature of adsorbate and of the nature of the bonded layer as well. The results obtained suggest penetration of the adsorbate molecules into the bonded layer and the importance of this process in the retention mechanism in gas chromatography. Energy of the dispersion interactions with the surface decreases in the following order: n-C16H33(CH3)2Si- > n-C8H17(CH3)2Si- > [(CH3)3SiO]2Si(CH3)-(CH2)10(CH3)2Si- > -[[(CH3)2SiO]2]x-(CH3)2Si-. Energy of the electrostatic and hydrogen bonding interactions with the surface, as assessed from the adsorption of benzene and diethyl ether molecules, decreases in the opposite direction, indicating that alkyl-silicas are less polar adsorbents than methylsiloxy-silicas.     

Photoassisted adsorption of allylamine and 1-butene on H:Si(111) studied by surface vibrational spectroscopies

Ultraviolet photoassisted adsorption of terminally double-bonded molecules, allylamine (CH2=CH-CH2-NH2) and 1-butene (CH2=CH-CH2-CH3), on hydrogen-terminated silicon (111) surface was attempted to obtain adsorbates covalently terminating the surface Si atoms. The adsorption process was monitored by high-resolution electron energy loss spectroscopy, multiple internal infrared reflection-absorption spectroscopy, and Auger electron spectroscopy. Allylamine adsorbates emerged upon delivery of allylamine gas under ultraviolet irradiation. The N-H bonds in allylamine were evidenced to survive over the photoadsorption process by vibrational analysis and by the reaction with ketene. CH3- groups were detected at low coverage, indicating anchoring of the organic moieties by the secondary (sec-) type carbon atoms, which were taken over by the primary (n-) type with increasing coverage. C-D bonds were detected after deposition on deuterium-terminated Si(111) upon incorporation of Si-terminating H into the hydrocarbon part of adsorbates. In the case of 1-butene, not only the C=C end but also the CH3- end of a molecule might attach on Si, resulting in emergence of adsorbates composed of CH2 groups. The newly obtained adsorbates are prospective as a material applied for nanolithography, fine electrochemistry, and nano-biotechnology.     

Solution and solid-state models of peptide CH...O hydrogen bonds

Fumaramide derivatives were analyzed in solution by (1)H NMR spectroscopy and in the solid state by X-ray crystallography in order to characterize the formation of CH...O interactions under each condition and to thereby serve as models for these interactions in peptide and protein structure. Solutions of fumaramides at 10 mM in CDCl(3) were titrated with DMSO-d(6), resulting in chemical shifts that moved downfield for the CH groups thought to participate in CH...O=S(CD(3))(2) hydrogen bonds concurrent with NH...O=S(CD(3))(2) hydrogen bonding. In this model, nonparticipating CH groups under the same conditions showed no significant change in chemical shifts between 0.0 and 1.0 M DMSO-d(6) and then moved upfield at higher DMSO-d(6) concentrations. At concentrations above 1.0 M DMSO-d(6), the directed CH...O=S(CD(3))(2) hydrogen bonds provide protection from random DMSO-d(6) contact and prevent the chemical shifts for participating CH groups from moving upfield beyond the original value observed in CDCl(3). X-ray crystal structures identified CH...O=C hydrogen bonds alongside intermolecular NH...O=C hydrogen bonding, a result that supports the solution (1)H NMR spectroscopy results. The solution and solid-state data therefore both provide evidence for the presence of CH...O hydrogen bonds formed concurrent with NH...O hydrogen bonding in these structures. The CH...O=C hydrogen bonds in the X-ray crystal structures are similar to those described for antiparallel beta-sheet structure observed in protein X-ray crystal structures.     

The role of the 5f orbitals in bonding, aromaticity, and reactivity of planar isocyclic and heterocyclic uranium clusters

The molecular and electronic structures, stabilities, bonding features and magnetic properties of prototypical planar isocyclic cyclo-U n X n ( n = 3, 4; X = O, NH) and heterocyclic cyclo-U n (mu 2-X) n ( n = 3, 4; X = C, CH, NH) clusters as well as the E@[ c-U 4(mu 2-C) 4], (E = H (+), C, Si, Ge) and U@[ c-U 5(mu 2-C) 5] molecules including a planar tetracoordinate element E (ptE) and pentacoordinate U (ppU) at the ring centers, respectively, have been thoroughly investigated by means of electronic structure calculation methods at the DFT level. It was shown that 5f orbitals play a key role in the bonding of these f-block metal systems significantly contributing to the cyclic electron delocalization and the associated magnetic diatropic (magnetic aromaticity) response. The aromaticity of the perfectly planar cyclo-U n X n ( n = 3, 4; X = O, NH), cyclo-U n (mu 2-X) n ( n = 3, 4; X = C, CH, NH), E@[ c-U 4(mu 2-C) 4], (E = H (+), C, Si, Ge) and U@[ c-U 5(mu 2-C) 5] clusters was verified by an efficient and simple criterion in probing the aromaticity/antiaromaticity of a molecule, that of the nucleus-independent chemical shift, NICS(0), NICS(1), NICS zz (0) and the most refined NICS zz (1) index in conjunction with the NICS scan profiles. Natural bond orbital analyses provided a clear picture of the bonding pattern in the planar isocyclic and heterocyclic uranium clusters and revealed the features that stabilize the ptE's inside the six- and eight-member uranacycle rings. The ptE's benefit from a considerable electron transfer from the surrounding uranium atoms in the E@[ c-U 4(mu 2-C) 4], (E = H (+), C, Si, Ge) and U@[ c-U 5(mu 2-C) 5] clusters justifying the high occupancy of the np orbitals of the central atom E.     

Periodic DFT calculations of the stability of Al/Si substitutions and extraframework Zn2+ cations in mordenite and reaction pathway for the dissociation of H2 and CH4

The local stability of Al atoms replacing Si in the zeolite framework is compared for all inequivalent tetrahedral (T) sites in mordenite. For Al/Si substitutions in two T sites the stable location of the compensating extraframework Zn(2+) cation forming a Lewis acid site is determined. In the most stable Zn-MOR structures Zn(2+) is located in a small ring (5MR, 6MR) containing two Al/Si substitutions. In less stable structures the Al atoms are placed at larger distances from each other and Zn(2+) interacts with only one Al site. The simulated adsorption of H(2) and CH(4) shows that adsorption strength decreases with increasing stability of the Zn(2+) Lewis site. A higher adsorption strength is observed for Zn(2+) deposited in the 5MR than for the 6MR. The reactivity of a series of stable Zn(2+) Lewis sites is tested via the dissociative adsorption of H(2) and CH(4). The heterolytic dissociation of the adsorbed molecule on the extraframework Zn(2+) cation produces a proton and an anion. The anion binds to Zn(2+) and proton goes to the zeolite framework, restoring a Br?nsted acid site. Because bonding of the anion to Zn(2+) is almost energetically equivalent for Zn(2+) in any of the extraframework positions the dissociation is governed by stabilizing bonding of the proton to the framework. Those structures which can exothermically accommodate the proton represent reaction pathways. Due to the repulsion between the proton and Zn(2+) the most favorable proton-accepting O sites are not those of the ring where Zn(2+) is deposited, but O sites close to the ring. Large differences are observed for neighboring positions in a- and b-directions and those oriented along the c-vector. Finally, among the stable Zn(2+) Lewis sites not all represent reaction pathways for dehydrogenation. For all of them the dissociation of H(2) is an exothermic process. In structures exhibiting the highest reactivity the Al/Si substitutions are placed at a large distance and the Zn(2+) cation interacts with O-atoms next to Al in the T4 site of the 5MR. This Lewis site is strong enough to break the C-H bond in the CH(4) molecule.     

Hydrolytic stability of organic monolayers supported on TiO2 and ZrO2

The hydrolytic stability of C18 monolayers supported on TiO2 and ZrO2 was studied. Three types of monolayers were prepared from the following octadecyl modifiers: (1) octadecyldimethylchlorosilane (C18H37Si(CH3)2Cl); (2) octadecylsilane (C18H37SiH3); and (3) octadecylphosphonic acid (C18H37P(O)(OH)2). The hydrolysis of the surfaces prepared was studied under static conditions at 25 and 65 degrees C at pH 1-10. On the basis of the loss of grafted material, the stability of the monolayers fall in the following range: C18H37P(O)(OH)2 > or = C18H37SiH3 > C18H37Si(CH3)2Cl. At 25 degrees C, monolayers from C18H37P(O)(OH)2 showed only approximately 2-5% loss in grafting density after one week at pH 1-10. The high stability of these monolayers was explained because of the strong interactions of the phosphonic acids with the substrates. Monolayers from C18H37Si(CH3)2Cl showed poor hydrolytic stability at any pH, which was explained because of the low stability of Ti-O-Si and Zr-O-Si bonds. Unlike monofunctional silanes, trifunctional silane (C18H37SiH3) yielded surfaces that showed good hydrolytic stability. This suggests that the stability of the monolayers from trifunctional silanes is primarily due to "horizontal" bonding (Si-O-Si or Si-OH...HO-Si) rather than due to bondingwith the matrix (M-O-Si). At 65 degrees C, all C18 surfaces become more susceptible to hydrolysis; however, the trend observed for 25 degrees C remained unchanged. Low-temperature nitrogen adsorption was used to study the adsorption properties of the monolayers as a function of their grafting density. The energy of adsorption interactions showed a significant increase as the grafting density of the monolayers decreased. The order of the alkyl groups in the monolayers, as assessed from CH2 stretching, decreased as the grafting density of the monolayers decreased.     

The nature of the interactions between Pt4 cluster and the adsorbates *H, *OH, and H2O

The nature of the interactions between the platinum cluster Pt4 and the adsorbates (*)H, (*)OH, and H2O, as well as the influence of these adsorbates on the electronic structure of the Pt4 cluster, was investigated by density functional theory (B3LYP, B3PW91, and BP86) together with the effective core potential MWB for the platinum atoms, and 6-311++G(d,p) and aug-cc-pVTZ basis set for the H and O atoms. Identification of the optimal spin multiplicity state and the preferential adsorption sites were also evaluated. Adsorption changes the cluster geometry significantly, but the relaxation effects on the adsorption energy are negligible. The adsorbates bind preferentially atop of the cluster, where high bonding energies were observed for the radical species. Adsorption is followed by a charge transfer from the Pt4 cluster toward radical adsorbates, but this charge transfer occurs in a reversed way when the adsorbate is H2O. In contrast with water, adsorption of the radicals (*)H and (*)OH on platinum causes a remarkable re-distribution of the spin density, characterized by a spin density sharing between the (*)H and (*)OH radicals and the cluster. The covalent character of the cluster-adsorbate interactions, determined by electron density topological analysis, reveals that the Pt4-H interaction is completely covalent, Pt4-OH is partially covalent, and Pt4-H2O is almost noncovalent.     

On the cooperativity of cation-pi and hydrogen bonding interactions

Quantum chemical calculations are performed to gauge the effect of cation-pi and hydrogen bonding interactions on each other. M-phenol-acceptor (M = Li (+) and Mg (2+); acceptor = H(2)O, HCOOH, HCN, CH(3)OH, HCONH(2) and NH(3)) is taken as a model ternary system that exhibits the cation-pi and hydrogen bonding interactions. Cooperativity is quantified and the computed positive cooperativity between cation-pi and hydrogen bonding interactions is rationalized through reduced variational space (RVS) and charge analyses.     

A comprehensive conformational analysis of tryptophan,its ionic and dimeric forms

Tryptophan is an essential amino acid, and understanding the conformational preferences of monomer and dimer is a subject of outstanding relevance in biological systems. An exhaustive first principles investigation of tryptophan ( W ) and its ionized counterparts cations (WC) , anions (WA) , and zwitterions (WZ) has been carried out. A comprehensive and systematic study of tryptophan dimer (WD) conformations resulted in about 62 distinct minima on the potential energy surface. The hydrogen bonds and a variety of noncovalent interactions such as OH‐π, NH‐π, CH‐π, CH‐O, and π‐π interactions stabilized different forms of tryptophan and its dimers. Over all in monomeric conformers which have NH‐O, hydrogen bonds showed higher stability than other conformers. A cursory analysis reveal that the most stable dimers stabilized by hydrogen bonding interactions while the less stable dimers showed aromatic side chain interactions. Protein Data Bank analysis of tryptophan dimers reveals that at a larger distance greater than 5 Å, T‐shaped orientations (CH‐π interactions) are more prevalent, while stacked orientations (π‐π interactions) are predominant at a smaller distance. © 2013 Wiley Periodicals, Inc.     

Azacalix[7]arene heptamethyl ether: preparation, nanochannel crystal structure, and selective adsorption of carbon dioxide

To investigate the solid-state complexation of nitrogen-bridged calixarene analogues, azacalix[7]arene heptamethyl ether 1 has been prepared by applying a "5 + 2"-fragment coupling approach using Buchwald-Hartwig aryl amination reaction aided by our previously devised temporal N-silylation protocol. X-ray crystallographic analysis revealed that azacalix[7]arene 1 adopted a highly distorted 1,2-alternate conformation in the solid state as a result of intramolecular NH/O hydrogen bonding interactions and steric repulsion between the methoxy groups. In the crystal, molecules of 1 are mutually interacted by intermolecular NH/O and CH/pi interactions to establish one-dimensional (1D) hexane-filled nanochannel crystal architecture. Similarly to our recently reported azacalix[6]arene 2, the desolvated crystalline powder material of 1 was capable of selectively and rapidly adsorbing CO2 among the four main components of the atmosphere. The adsorption capacity of 1 for CO2 nearly doubled as compared to that of 2 because of the formation of the 1D nanochannel with almost twice the volume of the latter.     

Water-soluble carbosilane dendrimers: synthesis biocompatibility and complexation with oligonucleotides; evaluation for medical applications

Novel amine- or ammonium-terminated carbosilane dendrimers of type nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe2)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe2}]x and nG-[Si{(CH2)3NH2}]x or nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe3 +I-)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe3 +I-}]x, and nG-[Si{(CH2)3NH3 +Cl-}]x have been synthesized and characterized up to the third generation by two strategies: 1) alcoholysis of Si--Cl bonds with amino alcohols and subsequent quaternization with MeI, and 2) hydrosilylation of allylamine with Si--H bonds of the dendritic systems and subsequent quaternization with HCl. Quaternized carbosilane dendrimers are soluble in water, although degradation is apparent due to hydrolysis of Si--O bonds. However, dendrimers containing Si--C bonds are water-stable. The biocompatibility of the second-generation dendrimers in primary cell cultures of peripheral blood mononuclear cells (PBMCs) and erythrocytes have been analyzed, and they show good toxicity profiles over extended periods. In addition, we describe a study on the interactions between the different carbosilane dendrimers and DNA oligodeoxynucleotides (ODNs) and plasmids along with a comparative analysis of their toxicity. They can form complexes with DNA ODNs and plasmids at biocompatible doses via electrostatic interaction. Also a preliminary transfection assay has been accomplished. These results demonstrate that the new ammonium-terminated carbosilane dendrimers are good base molecules to be considered for biomedical applications.     

Theory of late-transition-metal alkyl and heteroatom bonding: analysis of Pt, Ru, Ir, and Rh complexes

Density functional and correlated ab initio methods were used to calculate, compare, and analyze bonding interactions in late-transition-metal alkyl and heteroatom complexes (M-X). The complexes studied include: (DMPE)Pt(CH(3))(X) (DMPE = 1,2-bis(dimethylphosphino)ethane), Cp*Ru(PMe(3))(2)(X) (Cp* = pentamethylcyclopentadienyl), (DMPE)(2)Ru(H)(X), (Tp)(CO)Ru(Py)(X) (Tp = trispyrazolylborate), (PMe(3))(2)Rh(C(2)H(4))(X), and cis-(acac)(2)Ir(Py)(X) (acac = acetylacetonate). Seventeen X ligands were analyzed that include alkyl (CR(3)), amido (NR(2)), alkoxo (OR), and fluoride. Energy decomposition analysis of these M-X bonds revealed that orbital charge transfer stabilization provides a straightforward model for trends in bonding along the alkyl to heteroatom ligand series (X = CH(3), NH(2), OH, F). Pauli repulsion (exchange repulsion), which includes contributions from closed-shell d(π)-p(π) repulsion, generally decreases along the alkyl to heteroatom ligand series but depends on the exact M-X complexes. It was also revealed that stabilizing electrostatic interactions generally decrease along this ligand series. Correlation between M-X and H-X bond dissociation energies is good with R(2) values between 0.7 and 0.9. This correlation exists because for both M-X and H-X bonds the orbital stabilization energies are a function of the orbital electronegativity of the X group. The greater than 1 slope when correlating M-X and H-X bond dissociation energies was traced back to differences in Pauli repulsion and electrostatic stabilization.     

Purification of an oligonucleotide at high column loading by high affinity, low-molecular-mass displacers

New urea-functionalized silica stationary phases were prepared by a single-step surface modification through reaction of LiChrosorb Si100 (5 microm particle size) with a homologous series of alkoxysilanes, synthesized in our laboratory, with the general formula (CH3CH2O)3Si(CH2)3NHC(O)NH(CH2)nCH3, where n=4, 6 and 11. The modified silicas were characterized by elemental analysis of carbon and nitrogen, solid-state 29Si- and 13C-cross polarization magic angle spinning nuclear magnetic resonance and nitrogen adsorption isotherms at 77 K. Chromatographic evaluation of the three urea-functionalized silicas in 150x3.9 mm I.D. HPLC columns was carried out by the separation of a test mixture composed of uracil, acetophenone, benzene, toluene and naphthalene, using acetonitrile-water as mobile phase. These new stationary phases, with embedded polar urea groups, are very promising when compared with amide phases prepared by the conventional two-step modification process. A single-step reaction process silica modification is better for obtaining a well-characterized and homogeneous modified surface.     

HY沸石上的两种结构羟基的红外光谱研究

用红外光谱测定了碱度相近、构型不同的分子,如:氨、三乙胺和三正丁胺等及构型接近、碱度不同的分子,如:吡啶、2,6-二甲基吡啶和哌啶等在HY沸石的两种结构羟基上的吸附.通过升温热脱附的IR谱,观察了吸附分子的碱度和构型对质子酸强度的影响. 用红外光谱测定了HY沸石上HF和LF两种表面结构羟基吸附氨后的脱附热分别为22.2kcal/mol和18.9kcal/mol.     

Synthesis, crystal structures and magnetic behaviour of dimeric and tetrameric gadolinium carboxylates with trichloroacetic acid

The novel gadolinium(III) containing compounds (CH3NH3)2[Gd2(CCl3COO)6(H2O)6](CCl3COO)2.2CCl3COOH (1) and (NH3CH3)2[Gd4(OH)4(CCl3COO)10(H2O)6].2H2O (2) were synthesized and structurally characterized by X-ray crystallography. In the crystal structure of 1 the gadolinium ions are bridged by carboxylate groups to dimers with a Gd3+ -Gd3+ distance of 420.2(3) pm. The compound crystallizes in the triclinic space group P1. In the crystal structure of the Gd3+ ions are bridged by hydroxide ions and carboxylate groups to tetramers with Gd3+ -Gd3+ distances between 380.3(1) and 388.0(1) pm. The compound crystallizes in the triclinic space group P1. The magnetic behaviour of these two compounds as well as of Gd2(CCl3COO)6(bipy)2(H2O)2.4bipy (3) (bipy = 2,2'-bipyridyl) was investigated in the temperature range 1.77-300 K. The magnetic data for these compounds indicate weak antiferromagnetic interactions.     

卤代硅烷(R3SiX)与NR’3形成五配位硅化合物的加成反应

对R3SiX(R=H、CH3; X=F、Cl、Br、I)与NR’3 (R’=H、CH3)的加成物用量子化学密度泛函方法在B3LYP/6-31g(d,p)基组下(X原子采用cep-121g基组)进行了两种加成方式的研究. 一种是NR’3沿Si—X键轴向位置的加成, 另一种是NR’3沿Si—X键侧向接近的加成. 计算结果表明, 前者更稳定且更容易形成加成物; Si上斥电子基团不利于Si—N键的形成, 而N上斥电子基团则有利于Si—N键的形成; NH3-H3SiX系列和N(CH3)3-H3SiX系列均能以两种方式进行加成, NH3-H2(CH3)SiX系列仅能沿Si—X键轴向进行加成, 而NH3-H(CH3)2SiX和NH3-(CH3)3SiX 系列两种方式都不能进行加成; 在同系列加成产物中, 以X=Cl时所得加成物最稳定. 讨论了所有加成物中各键的性能、NBO电荷变化、取代基对加成物结构和稳定性的影响, 并对H3SiX(X=F、Cl、Br、I)与NH3及N(CH3)3加成物在有机溶剂中导电的可能性进行了讨论.     

Role of negative hyperconjugation and anomeric effects in the stabilization of the intermediate in SNV reactions

The role of negative hyperconjugation and anomeric and polar effects in stabilizing the XZHCbetaCalphaYY'- intermediates in SNV reactions was studied computationally by DFT methods. Destabilizing steric effects are also discussed. The following ions were studied: X = CH3O, CH3S, CF3CH2O and Y = Y' = Z = H (7b-7d), Y = Y' = H, Z = CH3O, CH3S, CF3CH2O (7e-7i), YY' = Meldrum's acid-like moiety (Mu), Z = H, (8b-8d), and YY' = Mu, Z = CH3O, CH3S, CF3CH2O (8e-8i). The electron-withdrawing Mu substituent at Calpha stabilizes considerably the intermediates and allows their accumulation. The hyperconjugation ability (HCA) (i.e., the stabilization due to 2p(Calpha) --> sigma*(Cbeta-X) interaction) in 8b-8d follows the order (for X, kcal/mol) CH3S (8.5) > CF3CH2O (7.6) approximately CH3O (7.5). The HCA in 8b-8d is significantly smaller than that in 7b-7d due to charge delocalization in Mu in the former. The calculated solvent (1:1 DMSO/H2O) effect is small. The stability of disubstituted ions (7e-7i and 8e-8i) is larger than that of monosubstituted ions due to additional stabilization by negative hyperconjugation and an anomeric effect. However, steric repulsion between the geminal Cbeta substituents destabilizes these ions. The steric effects are larger when one or both substituents are CH3S. The anomeric stabilization (the energy difference between the anti,anti and gauche,gauche conformers) in the disubstituted anions contributes only a small fraction to their total stabilization. Its order (for the following X/Z pairs, kcal/mol) is CF3CH2O/CH3S (8i, 4.9) > CF3CH2O/CH3O (8h, 3.9) > CH3O/CH3S (8g, 3.3) > CH3S/CH3S (8f, 2.9) > CH3O/CH3O (8e, 2.4). Significantly larger anomeric effects of ca. 8-9 kcal/mol are calculated for the corresponding conjugate acids.