SN2 Reactions with an Ambident Nucleophile A Benchmark Ab Initio Study of the CN-+ CH3Y [Y = F, Cl, Br, and I] Systems /
We characterize the Walden-inversion, front-side attack, and double-inversion SN2 pathways leading to Y- + CH3CN/CH3NC and the product channels of proton abstraction (HCN/HNC + CH2Y-), hydride-ion substitution (H- + YH2CCN/YH2CNC), halogen abstraction (YCN-/YNC- + CH3 and YCN/YNC + CH3-), and YHCN-/...
Elmentve itt :
| Szerzők: | |
|---|---|
| Dokumentumtípus: | Cikk |
| Megjelent: |
2022
|
| Sorozat: | JOURNAL OF PHYSICAL CHEMISTRY A
126 No. 6 |
| Tárgyszavak: | |
| doi: | 10.1021/acs.jpca.1c10448 |
| mtmt: | 32699789 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/24760 |
| LEADER | 02335nab a2200241 i 4500 | ||
|---|---|---|---|
| 001 | publ24760 | ||
| 005 | 20220726122120.0 | ||
| 008 | 220726s2022 hu o 0|| Angol d | ||
| 022 | |a 1089-5639 | ||
| 024 | 7 | |a 10.1021/acs.jpca.1c10448 |2 doi | |
| 024 | 7 | |a 32699789 |2 mtmt | |
| 040 | |a SZTE Publicatio Repozitórium |b hun | ||
| 041 | |a Angol | ||
| 100 | 1 | |a Kerekes Zsolt | |
| 245 | 1 | 0 | |a SN2 Reactions with an Ambident Nucleophile |h [elektronikus dokumentum] : |b A Benchmark Ab Initio Study of the CN-+ CH3Y [Y = F, Cl, Br, and I] Systems / |c Kerekes Zsolt |
| 260 | |c 2022 | ||
| 300 | |a 889-900 | ||
| 490 | 0 | |a JOURNAL OF PHYSICAL CHEMISTRY A |v 126 No. 6 | |
| 520 | 3 | |a We characterize the Walden-inversion, front-side attack, and double-inversion SN2 pathways leading to Y- + CH3CN/CH3NC and the product channels of proton abstraction (HCN/HNC + CH2Y-), hydride-ion substitution (H- + YH2CCN/YH2CNC), halogen abstraction (YCN-/YNC- + CH3 and YCN/YNC + CH3-), and YHCN-/YHNC- complex formation (YHCN-/YHNC- + 1CH2) of the CN- + CH3Y [Y = F, Cl, Br, and I] reactions. Benchmark structures and frequencies are computed at the CCSD(T)-F12b/aug-cc-pVTZ level of theory, and a composite approach is employed to obtain relative energies with sub-chemical accuracy considering (a) basis-set effects up to aug-cc-pVQZ, (b) post-CCSD(T) correlation up to CCSDT(Q), (c) core correlation, (d) relativistic effects, and (e) zero-point energy corrections. C-C bond formation is both thermodynamically and kinetically more preferred than N-C bond formation, though the kinetic preference is less significant. Walden inversion proceeds via low or submerged barriers (12.1/17.9(F), 0.0/4.3(Cl), -3.9/0.1(Br), and -5.8/-1.8(I) kcal/mol for C-C/N-C bond formation), front-side attack and double inversion have high barriers (30-64 kcal/mol), the latter is the lower-energy retention pathway, and the non-SN2 electronic ground-state product channels are endothermic (ΔH0 = 31-92 kcal/mol). © 2022 The Authors. Published by American Chemical Society. | |
| 650 | 4 | |a Fizikai kémia, polimertudomány, elektrokémia (szárazelemek, akkumulátorok, üzemanyagcellák, fémek korróziója, elektrolízis) | |
| 700 | 0 | 1 | |a Tasi Domonkos Attila |e aut |
| 700 | 0 | 1 | |a Czakó Gábor |e aut |
| 856 | 4 | 0 | |u http://publicatio.bibl.u-szeged.hu/24760/1/JPCA_126_889_2022.pdf |z Dokumentum-elérés |