Covalent Grafting of Silatranes to Carbon Interfaces

Peureux, Charles; Jouikov, Viatcheslav

doi:10.1002/chem.201403091

Cited by 17 publications

(15 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We have recently shown that when a metallatrane carries a relatively hard to ionize 1-substituent, electron withdrawal upon oxidation can directly affect this hyperbond, resulting in persistent cation radicals [10][11][12] with the spin localized inside the atrane cage on a practically planar N atom. 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).…”

mentioning

confidence: 99%

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

2018

Self Cite

View full text Add to dashboard Cite

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.

show abstract

mentioning

confidence: 99%

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

2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…Electrochemical oxidation of hypervalent metallatranes XM(OCH 2 CH 2 ) 3 N( I,w ith M = Si, Ge, Sn) has been shown to produce radicalc ations (RCs) possessing au nique structure and having ag reat promisef or the potentiala pplications. [1][2][3][4][5][6][7] To cite af ew,t hese might be an ew type of molecular wires, spin switches,a nd electromechanicals ystems. [4c, 5] Their potential in surfacer esearch has been demonstratedf or corrosion protection of metals [7] and functional capping of carbonaceousi nterfaces.…”

Section: Introductionmentioning

confidence: 99%

“…[4c, 5] Their potential in surfacer esearch has been demonstratedf or corrosion protection of metals [7] and functional capping of carbonaceousi nterfaces. [1] This raising interest to the redox chemistry of metallatranes is impeded by as ubstantial gap between the levels of experimental and theoretical works in this field. Remarkably, to date there were even no attempts to calculate the redox potentials of intramolecular complexes of the Group 14 elements, including metallatranes,t hat are anomalously sensitivet ot he media (solvent) effects.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…To cite a few, these might be a new type of molecular wires, spin switches, and electromechanical systems . Their potential in surface research has been demonstrated for corrosion protection of metals and functional capping of carbonaceous interfaces …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Sidorkin

Belogolova

Wang

et al. 2017

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Using 18 silatranes XSi(OCH CH ) N (1) as examples, the potentials of electrochemical oxidation E of the hypervalent compounds of Si were calculated for the first time at the ab initio and DFT levels. The experimental peak potentials E (acetonitrile) show an excellent agreement (MAE=0.03) with the MP2//B3PW91 calculated E (C-PCM). Radical cations of 1 reveal a stretch isomerism of the N→Si dative bond. Localization of the spin density (SD) on the substituent X and the short (s) coordination contact Si⋅⋅⋅N (d <2.13 Å) along with the high five-coordinate character of Si are typical for the first isomer 1 , whereas the second one, 1 , has a longer (l) Si⋅⋅⋅N distance (d >3.0 Å), the four-coordinate Si and the SD localized on the silatrane nitrogen atom N . The vertical model of adiabatic ionization (1→1 or 1→1 ) was developed. It allows, in accordance with an original experimental test (electrooxidation of 1 in the presence of ferrocene), a reliable prediction of the most probable pathways of the silatrane oxidation. The reliable relationships of E (1) with the strength characteristics of the dative contact N→Si were revealed.

show abstract

Anisyl-, aminophenyl-, and naphthylmethylsilatranes revisited

Wang

Romanovs

Spura

et al. 2016

Chem Heterocycl Comp

View full text Add to dashboard Cite

International audienceThree Si-substituted silatranes were synthesized in order to rectify their structure with particular attention to the length of the N-Si intramolecular dative bond. DFT calculations of potential energy profile as a function of the N-Si distance and the structure of HOMO were considered. The latter was found to vary its localization depending on the electron-donating properties of the substituent and the N-Si distance

show abstract

Covalent Grafting of Silatranes to Carbon Interfaces

Cited by 17 publications

References 28 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

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

Anisyl-, aminophenyl-, and naphthylmethylsilatranes revisited

Contact Info

Product

Resources

About