Ion-Pair SN2 Reaction of OH- and CH3Cl: Activation Strain Analyses of Counterion and Solvent Effects

被引：16

作者：

Laloo, Jalal Z. A. ^{[1
]}

Rhyman, Lydia ^{[1
,2
]}

Larranaga, Olatz ^{[3
,4
]}

Ramasami, Ponnadurai ^{[1
,2
]}

Bickelhaupt, F. Matthias ^{[5
,6
]}

de Cozar, Abel ^{[3
,4
,5
,7
]}

机构：

[1] Univ Mauritius, Fac Sci, Dept Chem, Computat Chem Grp, Reduit 80837, Mauritius

[2] Univ Johannesburg, Dept Appl Chem, Doornfontein Campus, ZA-2028 Johannesburg, South Africa

[3] Univ Basque Country, UPV EHU, Fac Quim, Dept Quim Organ 1, PK 1072, San Sebastian 20018, Spain

[4] DIPC, PK 1072, San Sebastian 20018, Spain

[5] Vrije Univ Amsterdam, ACMM, Dept Theoret Chem, Boelelaan 1083, NL-1081 HV Amsterdam, Netherlands

[6] Radboud Univ Nijmegen, Inst Mol & Mat, Heyendaalseweg 135, NL-6525 AJ Nijmegen, Netherlands

[7] Ikerbasque, Basque Fdn Sci, Bilbao 48013, Spain

来源：

CHEMISTRY-AN ASIAN JOURNAL | 2018年 / 13卷 / 09期

关键词：

activation strain model; density functional calculations; ion pairs; nucleophilic substitution; solvent effects; MAINGROUP-ELEMENT HYDRIDES; DENSITY-FUNCTIONAL THEORY; MOLECULAR-ORBITAL THEORY; AB-INITIO BENCHMARK; GAS-PHASE; NUCLEOPHILIC-SUBSTITUTION; CATION AFFINITIES; OXIDATIVE ADDITION; CHEMICAL-REACTIONS; SN2; REACTIONS;

D O I：

10.1002/asia.201800082

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We have theoretically studied the non-identity S(N)2 reactions of MnOH(n-1)+CH3Cl (M+=Li+, Na+, K+, and MgCl+; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M+ and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (S(N)2-b) and frontside (S(N)2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.

引用

页码：1138 / 1147

页数：10

共 50 条

[1] Activation Strain Analyses of Counterion and Solvent Effects on the Ion-Pair SN2 Reaction of NH2-and CH3Cl
Savoo, Nandini
Laloo, Jalal Z. A.
Rhyman, Lydia
Ramasami, Ponnadurai
Bickelhaupt, F. Matthias
Poater, Jordi
[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY, 2020, 41 (04) : 317 - 327
[2] Ion-Pair SN2 Substitution: Activation Strain Analyses of Counter-Ion and Solvent Effects
Laloo, Jalal Z. A.
Rhyman, Lydia
Ramasami, Ponnadurai
Bickelhaupt, F. Matthias
de Cozar, Abel
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (13) : 4431 - 4439
[3] ABINITIO STUDY OF THE SN2 REACTIONS OF OH- AND OOH- WITH CH3CL
EVANSECK, JD
BLAKE, JF
JORGENSEN, WL
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) : 2349 - 2353
[4] Solvation effects on the SN2 reaction between CH3Cl and Cl- in water
Ensing, B
Meijer, EJ
Blöchl, PE
Baerends, EJ
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (13): : 3300 - 3310
[5] ION-PAIR PROCESS IN CH3CL BY PHOTOIONIZATION
DIBELER, VH
WALKER, JA
[J]. JOURNAL OF CHEMICAL PHYSICS, 1965, 43 (05): : 1842 - &
[6] Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl
Kuechler, Erich R.
York, Darrin M.
[J]. JOURNAL OF CHEMICAL PHYSICS, 2014, 140 (05):
[7] Direct ab initio molecular dynamics study on a microsolvated SN2 reaction of OH-(H2O) with CH3Cl
Tachikawa, Hiroto
[J]. JOURNAL OF CHEMICAL PHYSICS, 2006, 125 (13):
[8] LOCAL ORBITAL DESCRIPTION OF CL- + CH3CL SN2 REACTION
TALATY, ER
SIMONS, G
[J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1978, 175 (MAR): : 213 - 213
[9] Effect of solvent polarity on the potential energy surface in the SN2 reaction of F- + CH3Cl
Satpathy, Lopamudra
Sahoo, Sagarika
Sahu, Prabhat K.
Behera, Pradipta K.
Mishra, Bijay K.
[J]. COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2019, 1150 : 18 - 25
[10] IDENTIFICATION OF AN ION-PAIR INTERMEDIATE IN AN SN2 REACTION
SNEEN, RA
LARSEN, JW
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (11) : 2593 - &

← 1 2 3 4 5 →