Dynamics for reaction of an ion pair in aqueous solution: Reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse

Yutaka Tsuji; Tetsuo Mori; John P. Richard; Tina L. Amyes; Mizue Fujio; Yuho Tsuno

doi:10.1021/ol015706s

Dynamics for reaction of an ion pair in aqueous solution: Reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse

Yutaka Tsuji
, Tetsuo Mori
, John P. Richard
, Tina L. Amyes
, Mizue Fujio
, Yuho Tsuno

Chemistry

National Institute of Technology, Kurume College
Kyushu University

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Matrix presented The sum of the rate constants for solvolysis and ¹⁸O-scrambling of 4-MeC₆H₄¹³CH(Me)¹⁸OC(O)C ₆F₅ in 50/50 (v/v) trifluoroethanol/water, k_solv + k_iso = 1.22 × 10^-5 s^-1, is larger than k_solv = 1.06 × 10^-5 s^-1 for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k_-1 = 7 × 10⁹ s^-1 for internal return by unimolecular collapse of the ion pair, which is significantly larger than k_Nu = 5 × 10⁸ M^-1 s^-1 for bimolecular nucleophilic addition of carboxylate anions to 4-MeC₆H₄CH(Me)⁺.

Original language	English
Pages (from-to)	1237-1240
Number of pages	4
Journal	Organic Letters
Volume	3
Issue number	8
DOIs	https://doi.org/10.1021/ol015706s
State	Published - Apr 19 2001

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title = "Dynamics for reaction of an ion pair in aqueous solution: Reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse",

abstract = "Matrix presented The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H413CH(Me)18OC(O)C 6F5 in 50/50 (v/v) trifluoroethanol/water, ksolv + kiso = 1.22 × 10-5 s-1, is larger than ksolv = 1.06 × 10-5 s-1 for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k-1 = 7 × 109 s-1 for internal return by unimolecular collapse of the ion pair, which is significantly larger than kNu = 5 × 108 M-1 s-1 for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+.",

author = "Yutaka Tsuji and Tetsuo Mori and Richard, \{John P.\} and Amyes, \{Tina L.\} and Mizue Fujio and Yuho Tsuno",

year = "2001",

month = apr,

day = "19",

doi = "10.1021/ol015706s",

language = "English",

volume = "3",

pages = "1237--1240",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Dynamics for reaction of an ion pair in aqueous solution

T2 - Reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse

AU - Tsuji, Yutaka

AU - Mori, Tetsuo

AU - Richard, John P.

AU - Amyes, Tina L.

AU - Fujio, Mizue

AU - Tsuno, Yuho

PY - 2001/4/19

Y1 - 2001/4/19

N2 - Matrix presented The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H413CH(Me)18OC(O)C 6F5 in 50/50 (v/v) trifluoroethanol/water, ksolv + kiso = 1.22 × 10-5 s-1, is larger than ksolv = 1.06 × 10-5 s-1 for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k-1 = 7 × 109 s-1 for internal return by unimolecular collapse of the ion pair, which is significantly larger than kNu = 5 × 108 M-1 s-1 for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+.

AB - Matrix presented The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H413CH(Me)18OC(O)C 6F5 in 50/50 (v/v) trifluoroethanol/water, ksolv + kiso = 1.22 × 10-5 s-1, is larger than ksolv = 1.06 × 10-5 s-1 for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k-1 = 7 × 109 s-1 for internal return by unimolecular collapse of the ion pair, which is significantly larger than kNu = 5 × 108 M-1 s-1 for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+.

UR - https://www.scopus.com/pages/publications/0035912317

U2 - 10.1021/ol015706s

DO - 10.1021/ol015706s

M3 - Article

C2 - 11348203

AN - SCOPUS:0035912317

SN - 1523-7060

VL - 3

SP - 1237

EP - 1240

JO - Organic Letters

JF - Organic Letters

IS - 8

ER -

Dynamics for reaction of an ion pair in aqueous solution: Reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse

Abstract

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