Predicting the reactivity of ambidentate nucleophiles and electrophiles using a single, general-purpose, reactivity indicator

被引:36
作者
Anderson, James S. M. [1 ]
Ayers, Paul W. [1 ]
机构
[1] McMaster Univ, Dept Chem, Hamilton, ON L8S 4M1, Canada
关键词
D O I
10.1039/b700960g
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We recently proposed a new reactivity indicator, termed the "general-purpose reactivity indicator'', Xi, which describes not only the classical reactivity paradigms, but also describes reactions that are neither frontier-orbital nor electrostatically controlled. This indicator was proposed to be especially useful for reactants with multiple reactive sites, especially if the nature of the reactivity at those sites was different. This suggests that this reactivity indicator is especially appropriate for ambidentate molecules; this paper confirms this hypothesis. The general-purpose reactivity indicator not only identifies the most reactive sites, it also identifies which substrates prefer which reactive sites. In particular, the reactivity indicator allows one to clearly distinguish which sites of an ambidentate molecule are most reactive when electron transfer from the attacking reagent is large ( a soft reagent) and which sites are most reactive when the attacking reagent is hard and highly charged ( so that electron transfer is relatively insignificant). To illustrate the efficacy of the indicator for nucleophiles we consider SCN-, SeCN-, NO2-, SO32-. For electrophiles we consider dimethyl carbonate, N-methyl-N-nitrosotoluene-p-sulfonamide (MNTS), and 1-chloro-2,4,6-trinitrobenzene (CNB).
引用
收藏
页码:2371 / 2378
页数:8
相关论文
共 53 条
[1]   Conceptual density-functional theory for general chemical reactions, including those that are neither charge- nor frontier-orbital-controlled. 1. Theory and derivation of a general-purpose reactivity indicator [J].
Anderson, James S. M. ;
Melin, Junia ;
Ayers, Paul W. .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2007, 3 (02) :358-374
[2]   Conceptual density-functional theory for general chemical reactions, including those that are neither charge- nor frontier-orbital-controlled. 2. Application to molecules where frontier molecular orbital theory fails [J].
Anderson, James S. M. ;
Melin, Junia ;
Ayers, Paul W. .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2007, 3 (02) :375-389
[3]   The dependence on and continuity of the energy and other molecular properties with respect to the number of electrons [J].
Ayers, Paul W. .
JOURNAL OF MATHEMATICAL CHEMISTRY, 2008, 43 (01) :285-303
[4]   The physical basis of the hard/soft acid/base principle [J].
Ayers, Paul W. .
FARADAY DISCUSSIONS, 2007, 135 :161-190
[5]   Elucidating the hard/soft acid/base principle: A perspective based on half-reactions [J].
Ayers, Paul W. ;
Parr, Robert G. ;
Pearson, Ralph G. .
JOURNAL OF CHEMICAL PHYSICS, 2006, 124 (19)
[6]   Indices for predicting the quality of leaving groups [J].
Ayers, PW ;
Anderson, JSM ;
Rodriguez, JI ;
Jawed, Z .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2005, 7 (09) :1918-1925
[7]   Perturbative perspectives on the chemical reaction prediction problem [J].
Ayers, PW ;
Anderson, JSM ;
Bartolotti, LJ .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2005, 101 (05) :520-534
[8]   An elementary derivation of the hard/soft-acid/base principle [J].
Ayers, PW .
JOURNAL OF CHEMICAL PHYSICS, 2005, 122 (14)
[9]   Perspective on "Density functional approach to the frontier-electron theory of chemical reactivity" - Parr RG, Yang W (1984) J Am Chem Soc 106: 4049-4050 [J].
Ayers, PW ;
Levy, M .
THEORETICAL CHEMISTRY ACCOUNTS, 2000, 103 (3-4) :353-360
[10]   Variational principles for describing chemical reactions: Condensed reactivity indices [J].
Ayers, PW ;
Morrison, RC ;
Roy, RK .
JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (20) :8731-8744