Bonding in germatranyl cation and germatranes

Ignatyev, Igor S.; Sundius, Tom; Vrazhnov, D. V.; Кочина, Т. А.; Воронков, М. Г.

doi:10.1016/j.jorganchem.2007.09.028

Cited by 22 publications

(10 citation statements)

References 26 publications

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“…Driven by the interest for germatranes, a remarkable effort in their synthetic chemistry was accomplished [6][7][8][9][10][11]. Chemical structure, molecular modeling and theoretical studies of these compounds [12][13][14][15][16] at different levels of theory, including correlated post-Hartee-Fock methods [16] allowed better understanding of the specificity of trans-annular N ? Ge bond and revealed the importance of interaction of Ge with all 5 substituents [13][14][15].…”

Section: Introductionmentioning

confidence: 99%

“…Chemical structure, molecular modeling and theoretical studies of these compounds [12][13][14][15][16] at different levels of theory, including correlated post-Hartee-Fock methods [16] allowed better understanding of the specificity of trans-annular N ? Ge bond and revealed the importance of interaction of Ge with all 5 substituents [13][14][15]. Biological activity of germatranes that is closely bound with the substitution character at Ge was extensively studied [1,[4][5][6]17,18].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Electrochemical oxidation of benzyl germatranes

Soualmi

Игнатович

Lukevics

et al. 2008

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrochemical oxidation of benzyl germatranes

Soualmi

Игнатович

Lukevics

et al. 2008

Journal of Organometallic Chemistry

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“…Highly polar C 3 symmetrical intramolecular silicon complexes XSi(OCH 2 CH 2 ) 3 N, i.e., silatranes ( XS ), are ideal candidates for such investigation. It is pertinent to note that the existence of a labile dative Si ← N bond in XS molecules (Figure ) predetermines their unique structure, unusual physical and chemical properties, as well as rich and various biological activities. − Mainly for this reason, the interest has not waned in the problem of the electronic structure of XS , its dependence on internal and external factors, and in the properties of the Si ← N coordination. ,− …”

Section: Introductionmentioning

confidence: 99%

“Outlaw” Dipole-Bound Anions of Intra-Molecular Complexes

et al. 2020

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Using the example of silatranes XSi(OCH 2 CH 2 ) 3 N (X = Me, H, F, Cl), XS, it was found that the effect of the dipolebound (DB) electron on the cage intramolecular complexes does not fit into the standard views. Upon the transition from XS to the DB anions XS − , the unusual shortening of the internuclear Si•••N distance is always observed. For X = Cl, it is equal to 0.15 Å, which is a record length for all DB anions known from the literature. The formation of DB anions with the cage structure has principal features, controlled not only by the "critical" value of the dipole moment (μ > 2.5 D), but also by a geometric factor, such as the degree of pyramidality of the N(CH 2 ) 3 moietythe positive end of the molecular dipole of XS. It was a surprise that the effect of the substituent X on the extent of the structural rearrangement in the process XS → XS − cannot be explained using the values of the electron detachment energy of XS − or the initial strength of the coordination Si ← N bond in XS. The unique sensitivity of the silatrane geometry to the addition of an excess electron is governed by the rate of increase of their dipole moment with the shortening of the dative Si ← N contact. The conclusions drawn are supported by the high-accuracy CCSD and CCSD(T) calculations and the experimental (RET-PES) data. There is no real reason to doubt that the peculiarities of the formation of DB anions of XS − can also be characteristic of many hundreds of their structural analogues XM(YCH 2 CH 2 ) 3 N (

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“…[9][10][11][12] For example, on the one hand, the arguments are against the covalent interaction between Si and N atoms in I. [9][10][11][12] For example, on the one hand, the arguments are against the covalent interaction between Si and N atoms in I.…”

Section: Introductionmentioning

confidence: 99%

“…However, discussion about the nature of the Si'D (D = N, O, S) coordination in ICSCs, including the Si'N nature in silatranes and therefore their electronic and orbital structure remains open. [9][10][11][12] For example, on the one hand, the arguments are against the covalent interaction between Si and N atoms in I. 9,10 On the other hand, the presence of the covalent component in the Si'N contact is evidenced.…”

Section: Introductionmentioning

confidence: 99%

Assignment of photoelectron spectra of silatranes: first ionization energies and the nature of the dative Si←N contact

Sidorkin

Belogolova

Doronina

2015

Phys. Chem. Chem. Phys.

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The problematic experimental photoelectron spectra of fluoro- and ethoxy-silatranes, XSi[OCH2CH2]3N (X = F and OEt), were assigned using theoretical spectra obtained by combining the OVGF//CCSD vertical ionization energies with the vibrational widths of the electronic transitions (linear vibronic coupling formalism, LVC). Taking into account the overlapping of the silatrane bands with the bands of probable impurities, bicyclic amines, (OH)XSi(OCH2CH2)2NCH2CH2OH, allowed us to reliably determine the position of the low-energy bands (at ∼9.7 eV for F- and at ∼9.2 eV for EtO-silatrane) associated with the ionization from a nitrogen lone pair level. For XSi[OCH2CH2]3N (X = F, H, OEt, Me), the correlation between the first vertical ionization energies, VIEs1, and the geometrical, electronic and orbital characteristics of the Si←N bonding was found. Its analysis suggests that the Si←N coordination in silatranes is orbital-controlled rather than charge-controlled.

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Bonding in germatranyl cation and germatranes

Cited by 22 publications

References 26 publications

Electrochemical oxidation of benzyl germatranes

Electrochemical oxidation of benzyl germatranes

“Outlaw” Dipole-Bound Anions of Intra-Molecular Complexes

Assignment of photoelectron spectra of silatranes: first ionization energies and the nature of the dative Si←N contact

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