Protonated Alcohols Are Examples of Complete Charge-Shift Bonds

被引：17

作者：

Anderson, Peter ^{[1
]}

Petit, Alban ^{[1
]}

Ho, Junming ^{[2
]}

Mitoraj, Mariusz Pawel ^{[3
]}

Coote, Michelle L. ^{[2
]}

Danovich, David ^{[4
,5
]}

Shaik, Sason ^{[4
,5
]}

Braida, Benoit ^{[6
,7
]}

Ess, Daniel H. ^{[1
]}

机构：

[1] Brigham Young Univ, Dept Chem & Biochem, Provo, UT 84602 USA

[2] Australian Natl Univ, Res Sch Chem, Canberra, ACT 0200, Australia

[3] Jagiellonian Univ, Fac Chem, PL-30060 Krakow, Poland

[4] Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel

[5] Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel

[6] Univ Paris 06, Sorbonne Univ, UMR 7616, LCT, F-75005 Paris, France

[7] CNRS, UMR 7616, LCT, F-75005 Paris, France

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 79卷 / 21期

基金：

澳大利亚研究理事会; 以色列科学基金会;

关键词：

AB-INITIO; VALENCE; DEPROTONATION; RADICALS; STABILITY; ORBITALS; COMPACT; ENERGY; MODEL; IONS;

D O I：

10.1021/jo501549q

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Accurate gas-phase and solution-phase valence bond calculations reveal that protonation of the hydroxyl group of aliphatic alcohols transforms the CO bond from a principally covalent bond to a complete charge-shift bond with principally no-bond character. All bonding in this charge-shift bond is due to resonance between covalent and ionic structures, which is a different bonding mechanism from that of traditional covalent bonds. Until now, charge-shift bonds have been previously identified in inorganic compounds or in exotic organic compounds. This work showcases that charge-shift bonds can occur in common organic species.

引用

页码：9998 / 10001

页数：4

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