| 000 | 04204nlm1a2200421 4500 | ||
|---|---|---|---|
| 001 | 663220 | ||
| 005 | 20231030041847.0 | ||
| 035 | _a(RuTPU)RU\TPU\network\34389 | ||
| 090 | _a663220 | ||
| 100 | _a20210201a2020 k y0engy50 ba | ||
| 101 | 0 | _aeng | |
| 102 | _aGB | ||
| 135 | _adrcn ---uucaa | ||
| 181 | 0 | _ai | |
| 182 | 0 | _ab | |
| 200 | 1 |
_aDiaryliodonium as a double ?-hole donor: the dichotomy of thiocyanate halogen bonding provides divergent solid state arylation by diaryliodonium cations _fN. S. Soldatova, P. S. Postnikov, V. V. Suslonov [et al.] |
|
| 203 |
_aText _celectronic |
||
| 300 | _aTitle screen | ||
| 330 | _aX-ray crystallography data revealed the dichotomy of thiocyanate-involving noncovalent interactions in [Ar1Ar2I](SCN), as reflected in the generation of two types of supramolecular aggregates: (i) previously unreported 4-membered heterotetramers (Ar1/Ar2 = 4-ClC6H4/2,4,6-(MeO)3C6H2, 4-BrC6H4/2,4,6-(MeO)3C6H2; 2 examples) featuring exclusively halogen bond (XB) N-XB-bound SCN− anions, and (ii) the 8-membered cyclic heterotetramers (Ar1/Ar2 = Ph/Ph, Ph/2,4,6-(MeO)3C6H2, 4-FC6H4/2,4,6-(MeO)3C6H2, 3,5-Me2C6H3/4-MeOC6H4, 3,5-Me2C6H3/2,4,6-(MeO)3C6H2; 5 examples) with two N,S-XB-bound thiocyanates featuring both S⋯I and N⋯I noncovalent contacts. In all cases, the IIII centers function as a double σ-hole donor to provide two directional XBs. The XB preorganization affects the chemoselectivity of the thiocyanate arylation in the solid-state: the heating of [Ar1Ar2I](SCN) exhibiting either N-, or N,S preorganized XBs leads to extremely rare N-arylation or the conventional S-arylation, respectively. The charge-assisted XBs in [Ar1Ar2I](SCN) were studied using density functional theory (DFT) calculations combined with a molecular electrostatic potential surface analysis and the quantum theory of atoms in molecules (QTAIM). Competition between the N- and N,S-XB interactions was studied, including the recognition of energy differences between the I⋯N and I⋯S contacts. The computational data were useful to rationalize the divergent solid-state N- or S-arylation of thiocyanates. | ||
| 333 | _aРежим доступа: по договору с организацией-держателем ресурса | ||
| 461 | _tOrganic Chemistry Frontiers | ||
| 463 |
_tVol. 7, iss. 16 _v[P. 2230-2242] _d2020 |
||
| 610 | 1 | _aэлектронный ресурс | |
| 610 | 1 | _aтруды учёных ТПУ | |
| 701 | 1 |
_aSoldatova _bN. S. _gNataljya Sergeevna |
|
| 701 | 1 |
_aPostnikov _bP. S. _corganic chemist _cAssociate Professor of Tomsk Polytechnic University, Candidate of chemical sciences _f1984- _gPavel Sergeevich _2stltpush _3(RuTPU)RU\TPU\pers\31287 |
|
| 701 | 1 |
_aSuslonov _bV. V. _cChemist _cJunior Researcher of Tomsk Polytechnic University _f1992- _gVitaly Valerjevich _2stltpush _3(RuTPU)RU\TPU\pers\47036 |
|
| 701 | 1 |
_aKissler _bT. Yu. _gTroyana |
|
| 701 | 1 |
_aIvanov _bD. M. _cChemist _cSenior researcher of Tomsk Polytechnic University, Candidate of chemical sciences _f1992- _gDaniil Mikhaylovich _2stltpush _3(RuTPU)RU\TPU\pers\47038 |
|
| 701 | 1 |
_aYusubov _bM. S. _cchemist _cProfessor of Tomsk Polytechnic University, Doctor of chemical sciences _f1961- _gMekhman Suleiman-Ogly (Suleimanovich) _2stltpush _3(RuTPU)RU\TPU\pers\31833 |
|
| 701 | 1 |
_aGalmes _bB. _gBartomeu |
|
| 701 | 1 |
_aFrontera _bA. _gAntonio |
|
| 701 | 1 |
_aKukushkin _bV. Yu. _gVadim |
|
| 712 | 0 | 2 |
_aНациональный исследовательский Томский политехнический университет _bИсследовательская школа химических и биомедицинских технологий _bНаучно-исследовательский центр "Онкотераностика" _h8442 _2stltpush _3(RuTPU)RU\TPU\col\27561 |
| 712 | 0 | 2 |
_aНациональный исследовательский Томский политехнический университет _bИсследовательская школа химических и биомедицинских технологий _c(2017- ) _h8120 _2stltpush _3(RuTPU)RU\TPU\col\23537 |
| 801 | 2 |
_aRU _b63413507 _c20211216 _gRCR |
|
| 856 | 4 | _uhttps://doi.org/10.1039/D0QO00678E | |
| 942 | _cCF | ||