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排序方式: 共有145条查询结果,搜索用时 312 毫秒
1.
Liliana Cseh Carol Csunderlik Ingo Pantenburg Gerd Meyer Otilia Costisor 《无机化学与普通化学杂志》2003,629(6):985-988
The complex Co(C14H13NO)2Cl2 with the protonated N‐salicylidene‐p‐toluidine ligand was synthesized from an ethanolic solution of CoCl2·6H2O and N‐salicylidene‐p‐toluidine. The crystal structure was determined from X‐ray single crystal data (monoclinic, space group Cc, a = 1496.2(3) pm, b = 1257.4(4) pm, c = 1544.6(3) pm, β = 115.01(1)°, Z = 4). Co2+ adopts a distorted tetrahedral geometry. The UV‐Vis and IR spectra of the complex are discussed. 相似文献
2.
I. Labádi E. Pál R. Tudose O. Costisor 《Journal of Thermal Analysis and Calorimetry》2006,83(3):681-686
The
thermal behaviour of the mixed-ligand complexes of cobalt(II) and copper(I)
ions with antipyrine derivatives of 1,2-ethanediamine or piperazine (BAMP
and TAMEN), with water and with 2-mercapto-benzothiazole (Hmbt) was investigated.
The complexes contain 2-mercaptobenzothiazole (Hmbt, in the case of cobalt(II)
ion) or dimercaptobenzothiazine (mbt–mbt, in the case of copper(I) ion)
molecules as ligands and perchlorate (ClO4–) or
thiocyanate (SCN – ) ion as counterion. By heating, water and ligands
release the solid phase at lower temperature. At higher temperatures process
of different organic reactions of ligands (e.g. polymerization, polycondensation)
could be suggested to interpret the relative high final mass values. 相似文献
3.
Bouchoux G Defaye D McMahon T Likholyot A Mó O Yáñez M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(13):2900-2909
The various protonated forms of phenol (1), catechol (2), resorcinol (3), and hydroquinone (4) were explored by ab initio quantum chemical calculations at the MP2/6-31G(d) and B3LYP/6-31G(d) levels. Proton affinities (PA) of 1-4 were calculated by the combined G2(MP2,SVP) method, and their gas-phase basicities were estimated after calculation of the change in entropy on protonation. These theoretical data were compared with the corresponding experimental values determined in a high-pressure mass spectrometer. This comparison confirmed that phenols are essentially carbon bases and that protonation generally occurs in a position para to the hydroxyl group. Resorcinol is the most effective base (PA = 856 kJ mol-1) due to the participation of both oxygen atoms in the stabilization of the protonated form. Since protonation is accompanied by a freezing of the two internal rotations, a significant decrease in entropy is observed. The basicity of catechol (PA = 823 kJ mol-1) is due to the existence of an intramolecular hydrogen bond, which is strengthened upon protonation. The lower basicity of hydroquinone (PA = 808 kJ mol-1) is a consequence of the fact that protonation necessarily occurs in a position ortho to the hydroxyl group. When the previously published data are reconsidered and a corrected protonation entropy is used, a proton affinity value of 820 kJ mol-1 is obtained for phenol. 相似文献
4.
Jenny?ZevallosEmail author Alejandro?Toro-Labbé Otilia?Mó Manuel?Yá?ez 《Structural chemistry》2005,16(3):295-303
High level ab initio and density functional theory calculations have been carried out to investigate the relative stability of the different conformers of hyponitrous acid and its mono- and dithio-derivatives. Geometries and vibrational frequencies were obtained at the B3LYP/6-311+G(d,p) level and final energies through B3LYP/6-311++G(3df,2pd) single point calculations. The reliability of this theoretical scheme has been assessed by comparing these DFT results with those obtained at the G3 level of theory, for some suitable cases. The cis conformers of hyponitrous acid and its mono- and dithio-derivatives are systematically more stable than the
trans ones because in the cis conformation a dative interaction between the nitrogen-lone pairs and the σNX^* antibonding orbital is significantly favored. Quite interestingly, in general, the conformers presenting an intramolecular hydrogen bond (IHB) are not the global minima of the corresponding potential energy surfaces and only for hyponitrous acid the conformer with a OH ⋅s O IHB is slightly more stable than the cis conformer without IHB. The low stability of the tautomers with IHB is closely related with another weak intramolecular interaction which involves the lone-pairs of the chalcogen atoms and the πNN* antibondig orbital, and which is significantly perturbed when the IHB is formed. 相似文献
5.
Dr. M. Merced Montero‐Campillo Prof. Al Mokhtar Lamsabhi Prof. Otilia Mó Prof. Manuel Yáñez 《Chemphyschem》2013,14(5):915-922
The UV/Vis spectra of selected substituted subporphyrazines (SubPz) and subphthalocyanines (SubPc) with aluminum and gallium as central atoms are analyzed through time‐dependent DFT calculations in chloroform. The results are compared with previous results with boron as the central atom to analyze the photochemical properties of these two families of compounds on varying the metal along the same group. The absorptions of SubPz (Al, Ga) are redshifted or blueshifted with respect to SubPz (B) depending on the nature of the R substituents of the molecule, whereas the absorptions of SubPc (Al, Ga) structures are redshifted and with smaller energy gaps with respect to SubPc (B) for all kinds of R substituents. Looking at their absorption spectra, these systems with aluminum and gallium may also have, as in the case of boron, promising photochemical properties. 相似文献
6.
An analysis of the effects induced by F, Cl, and Br-substituents at the α-position of both, the hydroxyl or the amino group for a series of amino-alcohols, HOCH2(CH2)nCH2NH2 (n = 0–5) on the strength and characteristics of their OH···N or NH···O intramolecular hydrogen bonds (IMHBs) was carried out through the use of high-level G4 ab initio calculations. For the parent unsubstituted amino-alcohols, it is found that the strength of the OH···N IMHB goes through a maximum for n = 2, as revealed by the use of appropriate isodesmic reactions, natural bond orbital (NBO) analysis and atoms in molecules (AIM), and non-covalent interaction (NCI) procedures. The corresponding infrared (IR) spectra also reflect the same trends. When the α-position to the hydroxyl group is substituted by halogen atoms, the OH···N IMHB significantly reinforces following the trend H < F < Cl < Br. Conversely, when the substitution takes place at the α-position with respect to the amino group, the result is a weakening of the OH···N IMHB. A totally different scenario is found when the amino-alcohols HOCH2(CH2)nCH2NH2 (n = 0–3) interact with BeF2. Although the presence of the beryllium derivative dramatically increases the strength of the IMHBs, the possibility for the beryllium atom to interact simultaneously with the O and the N atoms of the amino-alcohol leads to the global minimum of the potential energy surface, with the result that the IMHBs are replaced by two beryllium bonds. 相似文献
7.
I.?LabádiEmail author Zs.?Czibulya R.?Tudose O.?Costisor 《Journal of Thermal Analysis and Calorimetry》2004,78(3):965-972
Parent and mixed ligand complexes of cobalt(II) and copper(II) ions with N,N-bis-(4-antipyrylmethyl)piperazine or N,N-tetra(4-antipyryl-methyl)-1,2-diaminoethane or/and imidazole as ligand and ClO
4
–
or SCN– as counterion were synthesised and their thermal behaviour was investigated.This work was performed in the framework of cooperation between the Hungarian Academy of Sciences and Romanian Academy and was supported financially, in part, by the Hungarian Scientific Research Foundation (OTKA T 029554). 相似文献
8.
Del Bene JE Alkorta I Elguero J Mó O Yáñez M 《The journal of physical chemistry. A》2010,114(48):12775-12779
Ab initio equation-of-motion coupled cluster (EOM-CCSD) one-bond spin-spin coupling constants (1)J(B-N), (1)J(B-H), and (1)J(B-F) have been evaluated for complexes X:BH(n)F(3-n) with X = N(2), NCH, NCLi, H(2)CNH, NF(3), and NH(3), for n = 0-3. These complexes can be classified as either covalent or van der Waals complexes, on the basis of their binding energies and B-N distances. (1)J(B-N) for covalent complexes varies significantly from -19 to +9 Hz, whereas (1)J(B-N) is less than 2 Hz for van der Waals complexes. An absolute value of (1)J(B-N) of 3 Hz or greater indicates that the complex is covalently bonded, but a small value of this coupling constant does not necessarily mean that it is a van der Waals complex, in view of the variation among these complexes found for (1)J(B-N) as a function of the B-N distance. Deformation of the boron acid upon complex formation and electron donation by the nitrogen base has opposing effects on both (1)J(B-H) and (1)J(B-F). These effects are relatively small in van der Waals complexes. In covalent complexes, electron donation has the dominant effect on (1)J(B-H), and on (1)J(B-F) in complexes with BH(2)F and BHF(2), but acid deformation has the dominant effect on (1)J(B-F) in complexes with BF(3). Values of both (1)J(B-H) and (1)J(B-F) reflect the van der Waals or covalent nature of the B-N bond. 相似文献
9.
Simultaneous Aromatic–Beryllium Bonds and Aromatic–Anion Interactions: Naphthalene and Pyrene as Models of Fullerenes,Carbon Single‐Walled Nanotubes,and Graphene 下载免费PDF全文
Dr. Marta Marín‐Luna Prof. Ibon Alkorta Prof. José Elguero Prof. Otilia Mó Prof. Manuel Yáñez 《Chemphyschem》2015,16(12):2680-2686
The possibility of forming stable BeR2:ArH:Y? (R=H, F, Cl; ArH=naphthalene, pyrene; Y=Cl, Br) ternary complexes in which the beryllium compounds and anions are located on the opposite sides of an extended aromatic system is explored by means of MP2/aug‐cc‐pVDZ ab initio calculations. Comparison of the electron‐density distribution of these ternary complexes with the corresponding BeR2:ArH and ArH:Y? binary complexes reveals the existence of significant cooperativity between the two noncovalent interactions in the triads. The energetic effects of this cooperativity are quantified by evaluation of the three‐body interaction energy Δ3E in the framework of the many‐body interaction‐energy (MBIE) approach. Although an essential component of the interaction energies is electrostatic and is well reflected in the changes in the molecular electrostatic potential of the aromatic system on complexation, strong polarization effects, in particular for the BeR2:ArH interactions, also play a significant role. The charge transfers associated with these polarization effects are responsible for significant distortion of both the BeR2 and the aromatic moieties. The former are systematically bent in all the complexes, and the latter are curved to a degree that depends on the nature of the R substituents of the BeR2 subunit. 相似文献
10.
Why Is the Spontaneous Deprotonation of [Cu(uracil)2]2+ Complexes Accompanied by Enolization of the System? 下载免费PDF全文
Oriana Brea Prof. Manuel Yáñez Prof. Otilia Mó Dr. Al Mokhtar Lamsabhi 《Chemphyschem》2015,16(11):2375-2382
The reaction‐force formalism is applied to carry out a detailed analysis of the mechanisms behind the enolization processes undergone by the complexes formed on interaction of uracil dimers with Cu2+ ions after spontaneous deprotonation of the resulting complexes. These enolization processes apparently involve a single proton transfer (PT) from an NH group to a carbonyl group of the same uracil moiety, which should involve a rather high activation barrier that prevents the process occurring. However, the reaction‐force, chemical‐potential, and electronic‐flux profiles unambiguously indicate that the actual mechanism involves three low‐barrier elementary steps, and this explains why enolization of the [Cu(uracil?H)(uracil)]+ complexes is a highly facile, assisted PT process. All of the observed PT processes show a typical profile for both the chemical potential and the electronic flux associated with the bond‐breaking and the bond‐formation processes. 相似文献