Electrochemical Oxidation and Radical Cations of Structurally Non‐rigid Hypervalent Silatranes: Theoretical and Experimental Studies

Sidorkin, V. F.; Belogolova, Elena F.; Wang, Yu; Jouikov, Viatcheslav; Doronina, Evgeniya P.

doi:10.1002/chem.201604663

Cited by 19 publications

(23 citation statements)

References 75 publications

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“…However, a priori it is quite difficult to predict the site of the electron withdrawal from a given metallatrane not only knowing where the HOMO is located, but as well taking only the type of the HOMO in consideration. 14 For instance 2-thienyl-, 5-methyl-2-thienyl-, and 5bromo-2-thienyl-substituted germatranes release an electron from the thienyl substituent and not from their 3c-4e system. 11 In order to shed the light on this point, DFT modeling of 1-3 at the B3LYP/Lanl2DZ//HF/6-311G(d,p) level was undertaken.…”

Section: Syn Thesismentioning

confidence: 99%

“…10c,12 Such systems show a great promise for various modern applications, primarily for spin-commutating interfaces 13 and as potential electromechanical actuators. 11,12,14 Driven by the double interest for these compounds and continuing the works on the redox chemistry of intramolecular-coordinated derivatives of the elements of group 14 with pending 15 or included into a rigid structure 10, 11,16 coordinating groups, we envisaged a novel bis-metallatrane system with two fused atrane cages sharing a common nitrogen atom to form a 5c-6e hyperbond capped with two thienyl end-substituents (Scheme 1).…”

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Synthesis and Electrochemical Study of 1,1′-Thienyl-Substituted Fused Bis-germatranes with a Core 5c-6e Hyperbond

2018

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Novel fused bis-germatranes containing three hypercoordinated atoms (two Ge and one N) and substituted at the 1,1′-positions with bromo-thienyl groups [(3-bromo-2-thienyl)-, (3,5-dibromo-2-thienyl)-, and 3-(4-bromo)-2-thienyl] have been synthesized from the corresponding triethoxy(thienyl)germanes and tris(1,3-dihydroxypropan-2-yl)amine. The doubly degenerated HOMO and HOMO-1 in these compounds are localized on the thienyl substituents while a 5c-6e hyperbond of the bis-germatranyl core (C–Ge←N→Ge–C system) is only a lower lying HOMO-2. Square-wave pulse voltammetry in CH3CN/0.1 M Bu4NPF6 shows all three compounds to undergo reversible electrochemical oxidation affecting one thienyl substituent. The DFT B3LYP/Lanl2DZ//HF/6-311G(d,p) calculations of their cation radicals suggest the enhancement and shortening of the N→Ge intramolecular dative bond on the side of the oxidized thienyl unit because of the positive charge and the increased acceptor character of the latter; this is accompanied by the loss of the N→Ge dative bond on the side of the non-oxidized substituent and a substantial pyramidalization of the Ge atom.

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Section: Syn Thesismentioning

confidence: 99%

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confidence: 99%

Synthesis and Electrochemical Study of 1,1′-Thienyl-Substituted Fused Bis-germatranes with a Core 5c-6e Hyperbond

2018

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“…Silatranes, XSi(OCH 2 CH 2 ) 3 N (see Figure ), are highly polar (∼6–9 D) molecular cages with labile, internal Si ← N dative bonds. These bonds are strongly sensitive to the nature of their axial substituents, X, and to external factors. − An attractive interaction Si ← N in silatranes predetermines the peculiarity of their structure, unusual spectral characteristics, and reactivity as well as a wide spectrum of biological activity. , …”

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Dipole-Bound Anions of Intramolecular Complexes

Belogolova

Liu

Doronina

et al. 2018

J. Phys. Chem. Lett.

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Dipole-bound molecular anions are often envisioned as unperturbed neutral, polar molecules with single excess electrons. We report the observation of intramolecular structural distortions within silatrane molecules due to the formation of their dipole-bound anions. The combination of Rydberg electron transfer-anion photoelectron spectroscopy (RET-PES) and ab initio computational methodologies (CCSD and MP2) was used to study 1-hydro- (HS) and 1-fluoro- (FS) silatranes and their dipole bound anions, HS and FS. The vertical detachment energies (VDEs) of HS and FS were measured to be 48 and 93 meV, respectively. Ab initio calculations accurately reproduced these VDE values as well as their photoelectron spectral profiles. This work revealed significant shortening (by ∼0.1 Å) of dative Si ← N bond lengths when HS and FS formed dipole-bound anions, HS and FS. Detailed computational (Franck-Condon) analyses explained the absence of vibrational features in the photoelectron spectra of HS and FS.

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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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Electrochemical Oxidation and Radical Cations of Structurally Non‐rigid Hypervalent Silatranes: Theoretical and Experimental Studies

Cited by 19 publications

References 75 publications

Synthesis and Electrochemical Study of 1,1′-Thienyl-Substituted Fused Bis-germatranes with a Core 5c-6e Hyperbond

Synthesis and Electrochemical Study of 1,1′-Thienyl-Substituted Fused Bis-germatranes with a Core 5c-6e Hyperbond

Dipole-Bound Anions of Intramolecular Complexes

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

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