Alkoxyphenyltrichlorostannane35Cl NQR spectra

Фешин, В. П.; Dolgushin, G. V.; Lazarev, I. M.; Воронков, М. Г.

doi:10.1007/bf00748198

Cited by 3 publications

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“…Therefore, Table 2 shows the population of the valence p-orbitals and their 3p-components and the 35 Cl NQR parameters calculated from them only for one of these atoms. At the same time, the experimental 35 Cl NQR data indicate the inequivalence of electron distribution of all three chlorine atoms in this compound [1,7]. This discrepancy between the calculated and experimental data may indicate a different structure and, consequently, electron distribution in the molecule III in the gaseous and crystalline states of matter.…”

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confidence: 49%

“…The Cl 1 atom is in the trans position to the O 1 atom as indicates the value of Cl 1 SnO 1, close to 180º (Table 1). Nevertheless, the ratio of asymmetry parameters of EFG on the nuclei of atoms Cl 1 and Cl 2 (Cl 3 ) is opposite to those of axial and equatorial Cl atoms in the molecules of trigonal-bipyramidal structure [11][12][13]. This may be due to the influence of the O 2 atom in molecule III affecting the populations of 3p-components of valence p x and p y orbitals which in the Cl 1 atom become substantially different, while in Cl 2 and Cl 3 atoms are identical ( Table 2).…”

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confidence: 94%

“…The EFG asymmetry parameters η at the 35 Cl nuclei of the axial and equatorial Cl atoms in the molecule I differ only slightly, while the η value of equatorial Cl atom is too small, which is not characteristic of such atoms in the molecules of trigonal-bipyramidal structure [11][12][13]. According to the 35 Cl NQR spectrum registered at 77 K, the electron distribution of the equatorial chlorine atoms in this molecule differs only slightly.…”

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confidence: 99%

“…Investigation of 2-methoxyphenyltrichlorostannane by nuclear quadrupole resonance (NQR) on the 35 Cl nuclei has shown [1] that the Sn atom can be pentacoordinated through additional interaction with the oxygen atom of the methoxy group. For example, in the triplet 35 Cl NQR spectrum of 2-CH 3 OC 6 H 4 SnCl 3 at 77 K the low-frequency line (20.070 MHz) is considerably removed from the high-frequency doublet (21.762 and 21.674 MHz).…”

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Stereoelectronic structure of methoxyphenyltrichlorostannanes by the results of ab initio calculations

Фешин

Фешина

2012

Russ J Gen Chem

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The RHF/3-21G* and MP2/3-21G* levels were implemented for the study of the stereoelectronic structure of 2-and 4-methoxyphenyl-and 2,6-dimethoxyphenyltrichlorostannanes. In the 4-methoxyphenyltrichlorostannane the Sn atom is tetracoordinated, while in 2-methoxy-and 2,6-dimethoxyphenyltrichlorostannanes it is pentacoordinated due to the intramolecular interaction of the O atom with it. In this case a closure occurs of a 4-membered ring. In the last molecule, the Sn atom interacts almost exclusively with only one of the O atoms. The intramolecular interaction between the Sn and O atoms leads to the electron density transfer from C and H atoms of the methoxy groups as well as from the Sn atom to the atoms of its coordination polyhedron. As a result the electron density increases also on the O atom involved in this interaction.Investigation of 2-methoxyphenyltrichlorostannane by nuclear quadrupole resonance (NQR) on the 35 Cl nuclei has shown [1] that the Sn atom can be pentacoordinated through additional interaction with the oxygen atom of the methoxy group. For example, in the triplet 35 Cl NQR spectrum of 2-CH 3 OC 6 H 4 SnCl 3 at 77 K the low-frequency line (20.070 MHz) is considerably removed from the high-frequency doublet (21.762 and 21.674 MHz). The expansion of the Sn atom coordination in such compounds may result in either intra-or intermolecular interaction of the Sn and O atoms. In the NQR spectrum of 4-CH 3 OC 6 H 4 SnCl 3 which is incapable of such intramolecular interaction the splitting of the lines is relatively small (21.299, 21.204, 21.160, 21.008, 20.728 and 20.385 MHz). Apparently, the unit cell of this compound contains two crystallographically nonequivalent molecules. The relatively narrow range of frequencies of this spectrum and a small splitting of its lines indicate that the difference in the electron distribution of the chlorine atoms of this compound is insignificant. This allows us to conclude that the Sn atom is tetracoordinated and a significant intermolecular Sn←O interaction does not occur. Unfortunately, the asymmetry parameters of the electric field gradient (EFG) at the nuclei 35 Cl of these compounds were not measured.

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Stereoelectronic structure of methoxyphenyltrichlorostannanes by the results of ab initio calculations

Фешин

Фешина

2012

Russ J Gen Chem

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“…Therefore, the parameters of the 35 Cl NQR for these dimers were calculated only for one of them ( Table 2). The 35 Cl NQR parameters of the dimer IV are characteristic of the chlorine-containing compounds of the IVA group elements with trigonal-bipyramidal structure (e.g., see [15,16]). The parameters calculated for the dimers V and VI are typical of the chlorine atoms bonded with tetracoordinated atoms of these elements.…”

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Stereoelectronic structure of 1-methyl-3-(trichlorogermyl)propionic acid as found by Ab initio calculations

Фешин

Фешина

2012

Russ J Gen Chem

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Calculations of three structures of the 1-methyl-3-(trichlorogermyl)propionic acid molecule and its dimers were performed at the RHF/6-31G(d) level with the full geometry optimization. According to the calculations, in this molecule in a gaseous state the Ge atom is most likely pentacoordinated due to the Ge←O coordination interaction. The dimerization does not diminish, but slightly increases the strength of Ge←O coordination bond. At the formation of the Ge←O bond the electron density on the oxygen atom increases and on the Ge atom decreases. The comparison of the results of calculations with X-ray diffraction data and with the 35 Cl NQR spectrum shows that stereoelectronic structure of this compound in the crystalline and gaseous states are quite different.The XRD analysis of 1-methyl-3-(trichlorogermyl) propionic acid showed that Ge←:O interaction occurring in this molecule was much weaker than in the 3-(trichlorogermyl)propionamide, 2-methyl-3-(trichlorogermyl)propionic acid N,N-dimethylamide, and 1-(1-trichlorogermylethyl)pyrrolidone-2, but somewhat stronger than in the 3-(trichlorogermyl)propionic acid [1]. In the molecule of 1-methyl-3-(trichlorogermyl)propionic acid the coordination polyhedron of the Ge atom tends to transformation from the tetrahedral to a trigonal-bipyramidal structure, there is a noticeable trend to a differentiation of the bonds of Ge atom into axial and equatorial ones, namely, the Ge-Cl bond in trans position to oxygen atom is longer than the other two (Table 1). In the crystal, these molecules are bound into dimers by the O-H···O hydrogen bonds, which results in weakening of the coordination Ge←O bond in the dimer compared with the aforementioned molecule [1]. The nuclear quadrupole resonance (NQR) spectrum on the 35 Cl nuclei of this compound at 77 K (23.929, 22.870, and 22.078 MHz) indicates a substantial nonequivalence of all three Ge-Cl bonds. Such nonequivalence is not characteristic of the tetrahedral or trigonal-bipyramidal Ge atom. In this molecule the coordination polyhedron is of intermediate structure [2].To examine further the stereoelectronic structure of 1-methyl-3-(trichlorogermyl)propionic acid, the nature of coordination Ge←O bond in it, and the effect on it of dimerization, we performed quantum-chemical calculations of three possible structures of this molecule and its dimers by RHF/6-31G(d) method with the full geometry optimization using the GAUSSIAN 03W software [3]. The XRD structural data and 35 Cl NQR spectra of the 1-methyl-3-(trichlorogermyl)propionic acid were obtained in the crystalline state, where the molecules not always are in the energetically most favorable form (e.g., see [4,5]). Therefore, it seemed appropriate to explore stereoelectronic structure of this acid in the gaseous state and compare it with the existing XRD data and the 35 Cl NQR spectra. In the calculations, for the origin of the coordinate system the chlorine atom was chosen whose 35 Cl NQR parameters should be determined. The Zaxis of the system coincided with the direction of the ...

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10.1007/s11176-008-2010-1

2010

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Quantum-chemical calculations of systems Cl 4 M 6L and Cl 4 M 42L (M = Si, Ge) with full geometry optimization and with a fixed M 4L distance, as well as calculations of the individual components of the complexes are performed by the RHF/6-31G(d) and B3LYP/6-311+G(2d,p) methods. It is shown that in the crystal state the molecular form may differ from that most favored by energy. The total energy of transoctahedral complexes of GeCl 4 with organic ligands is lower than the sum of the energies of their constituent components, while that of analogous SiCl 4 complexes may be either lower or higher than the sum of the energies of their constituent components. Even though trigonal3bipyramidal complexes of MCl 4 with organic ligands are commonly energetically unfavorable, they still can form. The formation of MCl 4 complexes is affected substantially by intermolecular interactions in crystal.

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Alkoxyphenyltrichlorostannane35Cl NQR spectra

Cited by 3 publications

References 2 publications

Stereoelectronic structure of methoxyphenyltrichlorostannanes by the results of ab initio calculations

Stereoelectronic structure of methoxyphenyltrichlorostannanes by the results of ab initio calculations

Stereoelectronic structure of 1-methyl-3-(trichlorogermyl)propionic acid as found by Ab initio calculations

10.1007/s11176-008-2010-1

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