The Factors Determining Reactivity in Nucleophilic Substitution

Advances in Physical Organic Chemistry

Volumn 51, Issue , 2017, Pages 1-57

  Uggerud, Einar ^a  

^a UNIVERSITY OF OSLO   (Norway)

Author keywords

Gas phase ion chemistry; Linear free energy relationships; Marcus theory; Mass spectrometry; Nucleophilicity; Quantum chemical calculations; Reaction dynamics; Reaction mechanisms; SN2 reaction; Solvent effects

Indexed keywords

EID: 85028964547     PISSN: 00653160     EISSN: None     Source Type: Book Series    
DOI: 10.1016/bs.apoc.2017.07.001     Document Type: Chapter

References (260)

1. Le Bel, J.A., A propos de l' inversion optique de Walden. J Chim Phys 9 (1911), 323–324.
2. Lewis, G.N., Valence and the Structure of Atoms and Molecules. 1923, Chemical Catalog Co., New York.
3. London, F., Quantenmechanische Deutung Des Vorgangs Der Aktivierung. Z Elektrochem Angew Phys Chem 35 (1929), 552–555.
4. Hughes, E.D., Ingold, C.K., Patel, C.S., Influence of poles and polar linkings on the course pursued by elimination reactions. Part XVI. Mechanism of the thermal decomposition of quaternary ammonium compounds. J Chem Soc, 1933, 526–530.
5. Gleave, J.L., Hughes, E.D., Ingold, C.K., Mechanism of substitution at a saturated carbon atom. Part III. Kinetics of the degradations of sulphonium compounds. J Chem Soc, 1935, 236–244.
6. Walden, P., Über die gegenseitige Umwandlung optischer Antipoden. Ber Dtsch Chem Ges 29 (1896), 133–138.
7. Olson, A.R., The mechanism of substitution reactions. J Chem Phys 1 (1933), 418–423.
8. Ingold, C.K., Structure and Mechanism in Organic Chemistry. 1953, Cornell University Press, Ithaca, NY.
9. Streitwieser, A., Solvolytic displacement reactions at saturated carbon atoms. Chem Rev 56 (1956), 571–752.
10. Guthrie, R.D., System for symbolic representation of reaction mechanisms (Recommendations 1988). Pure Appl Chem 61 (1989), 23–56.
11. Guthrie, R.D., Jencks, W.P., IUPAC recommendations for the representation of reaction mechanisms. Acc Chem Res 22 (1989), 343–349.
12. Edwards, J.O., Pearson, R.G., The factors determining nucleophilic reactivities. J Am Chem Soc 84 (1962), 16–24.
13. Riveros, J.M., José, S.M., Takashima, K., Gas-phase nucleophilic displacement reactions. Adv Phys Org Chem 21 (1985), 197–240.
14. Laerdahl, J.K., Uggerud, E., Gas phase nucleophilic substitution. Int J Mass Spectrom 214 (2002), 277–314.
15. Gronert, S., Mass spectrometric studies of organic ion/molecule reactions. Chem Rev 101 (2001), 329–360.
16. Swain, C.G., Scott, C.B., Quantitative correlation of relative rates. Comparison of hydroxide ion with other nucleophilic reagents toward alkyl halides, esters, epoxides and acyl halides. J Am Chem Soc 75 (1953), 141–147.
17. Winstein, S., Savedoff, L.G., Smith, S., Stevens, I.D.R., Gall, J.S., Ion pairs, nucleophilicity and salt effects in bimolecular nucleophilic substitution. Tetrahedron Lett 1 (1960), 24–30.
18. Parker, A.J., 255. Solvation of ions. Part II. Dipolar aprotic solvents as media for nucleophilic substitution reactions at a saturated carbon atom. J Chem Soc, 1961, 1328–1337.
19. Hine, J., Weimar, R.D., Carbon basicity. J Am Chem Soc 87 (1965), 3387–3396.
20. N2 displacements. Proc Natl Acad Sci USA 82 (1985), 8288–8290.
21. o. J Am Chem Soc 92 (1970), 7354–7358.
22. −. J Chem Soc Chem Commun, 1973, 35–36.
23. Bohme, D.K., Mackay, G.I., Payzant, J.D., Activation energies in nucleophilic displacement reactions measured at 296 K. J Am Chem Soc 96 (1974), 4027–4028.
24. Tanaka, K., MacKay, G.I., Payzant, J.D., Bohme, D.K., Gas-phase reactions of anions with halogenated methanes at 297 +/− 2 K. Can J Chem 54 (1976), 1643–1659.
25. Olmstead, W.N., Brauman, J.I., Gas-phase nucleophilic displacement reactions. J Am Chem Soc 99 (1977), 4219–4228.
26. Lieder, C.A., Brauman, J.I., Detection of neutral products in gas-phase, ion-molecule reactions. J Am Chem Soc 96 (1974), 4028–4030.
27. Lieder, C.A., Brauman, J.I., A technique for detection of neutral products in gas-phase, ion-molecule reactions. Int J Mass Spectrom Ion Phys 16 (1975), 307–319.
28. Bartmess, J.E., Scott, J.A., McIver, R.T., Scale of acidities in the gas phase from methanol to phenol. J Am Chem Soc 101 (1979), 6046–6056.
29. Brauman, J., Han, C.-C., Carbon and proton basicity. J Am Chem Soc 110 (1988), 5611–5613.
30. McMahon, T.B., Heinis, T., Nicol, G., Hovey, J.K., Kebarle, P., Methyl cation affinities. J Am Chem Soc 110 (1988), 7591–7598.
31. Uggerud, E., Correlation between alkyl cation affinities and proton affinity—a means to understand the chemical properties of alkyl compounds. Eur Mass Spectrom 6 (2000), 131–134.
32. Uggerud, E., Nucleophilicity—periodic trends and connection to basicity. Chem A Eur J 12 (2006), 1127–1136.
33. Mulder, R.J., Fonseca Guerra, C., Bickelhaupt, F.M., Methyl cation affinities of neutral and anionic maingroup-element hydrides: trends across the periodic table and correlation with proton affinities. J Phys Chem A 114 (2010), 7604–7608.
34. Laurence, C., Gal, J.-F., Lewis Basicity and Affinity Scales: Data and Measurement. 2010, John Wiley & Sons, Chichester.
35. Ruiz, J.M., Mulder, R.J., Guerra, C.F., Bickelhaupt, F.M., Steric effects on alkyl cation affinities of maingroup-element hydrides. J Comput Chem 32 (2011), 681–688.
36. Lias, S.G., Bartmess, J.E., Liebman, J.F., Holmes, J.H., Levin, R.D., Mallard, W.G., Gas-phase ion and neutral thermochemistry. J Phys Chem Ref Data Monogr 17 (1988), 1–861.
37. Aue, D.H., Webb, H.M., Bowers, M.T., Quantitative relative gas-phase basicities of alkylamines. Correlation with solution basicity. J Am Chem Soc 94 (1972), 4726–4728.
38. Koppel, I., Mölder, U., Pikver, R., On relationship between ionization potentials and proton affinities in gas phase. Org React (Engl Ed) 20 (1980), 457–494.
39. Bartmess, J.E., Hinde, R.J., The gas-phase acidities of the elemental hydrides are functions of electronegativity and bond length. Can J Chem 83 (2005), 2005–2012.
40. Brønsted, J.N., Pedersen, K., Die katalytische Zersetzung des Nitramids und ihre physikalisch-chemische Bedeutung. Z Phys Chem 108 (1924), 185–235.
41. Bell, R.P., The theory of reactions involving proton transfers. Proc R Soc London Ser A 154 (1936), 414–429.
42. Evans, M.G., Polanyi, M., Further considerations on the thermodynamics of chemical equilibria and reaction rates. Trans Faraday Soc 32 (1936), 1333–1360.
43. Hammond, G.S., A correlation of reaction rates. J Am Chem Soc 77 (1955), 334–338.
44. Haberfield, P., Experimental method for estimating substituent effects on transition-state structure. J Am Chem Soc 93 (1971), 2091–2093.
45. Leffler, J.E., Parameters for the description of transition states. Science 117 (1953), 340–341.
46. Murdoch, J.R., Rate-equilibriums relations and proton-transfer reactions. J Am Chem Soc 94 (1972), 4410–4418.
47. Marcus, R.A., Chemical and electrochemical electron-transfer theory. Ann Rev Phys Chem 15 (1964), 155–196.
48. Marcus, R.A., Theoretical relations among rate constants, barriers, and Brønsted slopes of chemical reactions. J Phys Chem 72 (1968), 891–899.
49. Kubo, R., Toyozawa, Y., Application of the method of generating function to radiative and non-radiative transitions of a trapped electron in a crystal. Prog Theor Phys 13 (1955), 160–182.
50. Albery, W.J., Kreevoy, M.M., Methyl transfer reactions. Adv Phys Org Chem 16 (1978), 87–157.
51. Pellerite, M.J., Brauman, J.I., Intrinsic barriers in nucleophilic displacements. J Am Chem Soc 102 (1980), 5993–5999.
52. Pellerite, M.J., Brauman, J.I., Intrinsic barriers in nucleophilic displacements. A general model for intrinsic nucleophilicity toward methyl centers. J Am Chem Soc 105 (1983), 2672–2680.
53. N2 typique. Theor Chim Acta 14 (1969), 329–338.
54. N2 reactions through ab initio calculations. J Am Chem Soc 94 (1972), 6730–6738.
55. Duke, A.J., Bader, R.F.W., A Hartree-Fock SCF calculation of the activation energies for two SN2 reactions. Chem Phys Lett 10 (1971), 631–635.
56. Bader, R.F.W., Duke, A.J., Messer, R.R., Interpretation of the charge and energy changes in two nucleophilic displacement reactions. J Am Chem Soc 95 (1973), 7715–7722.
57. N2 reactions. Ab initio computations on HF and CI level. J Am Chem Soc 98 (1976), 4787–4793.
58. N2 transition states. 1. Geometries. J Am Chem Soc 103 (1981), 7692–7694.
59. N2 transition states. 2. Intrinsic barriers, rate-equilbrium relationships, and the Marcus equation. J Am Chem Soc 103 (1981), 7694–7696.
60. N2 reactions of halide anions with methyl halides: a high-level computational study. J Am Chem Soc 117 (1995), 2024–2032.
61. N2 reactions of halide anions with methyl halides: a high-level computational study. J Am Chem Soc 118 (1996), 6273–6284.
62. N2) reactions. J Am Chem Soc 106 (1984), 5356–5357.
63. Lee, I., Kim, C.K., Lee, B.-S., Ab initio molecular orbital studies of nonidentity allyl transfer reactions. J Comput Chem 16 (1995), 1045–1054.
64. N2 identity reactions. Correlation between nucleophilisity and proton affinity. J Chem Soc, Perkin Trans 2, 1999, 1459–1463.
65. N2 reactions and the periodic table. J Am Chem Soc 121 (1999), 7724–7725.
66. N2 reactions. J Org Chem 67 (2002), 5891–5895.
67. N2 reactions at neutral nitrogen: a hybrid DFT study. Int J Mass Spectrom 229 (2003), 199–208.
68. N2 reactions of halides with halodimethylamine. J Am Soc Mass Spectrom 15 (2004), 673–680.
69. 2): Marcus theory analyzed. J Phys Chem A 109 (2005), 10613–10628.
70. Chen, X., Brauman, J.I., Hydrogen bonding lowers intrinsic nucleophilicity of solvated nucleophiles. J Am Chem Soc 130 (2008), 15038–15046.
71. Ritchie, C.D., Nucleophilic reactivities toward cations. Acc Chem Res 5 (1972), 348–354.
72. Mayr, H., Patz, M., Scales of nucleophilicity and electrophilicity: a system for ordering polar organic and organometallic reactions. Angew Chem Int Ed 33 (1994), 938–957.
73. Mayr, H., Breugst, M., Ofial, A.R., Farewell to the HSAB treatment of ambident reactivity. Angew Chem Int Ed 50 (2011), 6470–6505.
74. Jencks, W.P., Carriuolo, J., Reactivity of nucleophilic reagents toward esters. J Am Chem Soc 82 (1960), 1778–1786.
75. Green, A.L., Sainsbury, G.L., Saville, B., Stansfield, M., The reactivity of some active nucleophilic reagents with organophosphorus anticholinesterases. J Chem Soc, 1958, 1583–1587.
76. Hoz, S., The a effect: on the origin of transition-state stabilization. J Org Chem 47 (1982), 3545–3547.
77. DePuy, C.H., Della, E.W., Filley, J., Grabowski, J.J., Bierbaum, V.M., Absence of an α-effect in the gas-phase nucleophilic reactions of hydroperoxide ion. J Am Chem Soc 105 (1983), 2481–2482.
78. N2 and E2 mechanisms and the gas-phase α-effect. J Am Chem Soc 131 (2009), 8227–8233.
79. Garver, J.M., Gronert, S., Bierbaum, V.M., Experimental validation of the α-effect in the gas phase. J Am Chem Soc 133 (2011), 13894–13897.
80. Patterson, E.V., Fountain, K.R., On gas phase α-effects. 1. The gas-phase manifestation and potential SET character. J Org Chem 71 (2006), 8121–8125.
81. Fountain, K.R., The size of the alpha-effects in methyl transfers correlate with Koopmans' theorem ionization potentials. J Phys Org Chem 18 (2005), 481–485.
82. Afzal, D., Fountain, K.R., Theoretical investigation of experimentally determined α-effects—the role of electronics. Can J Chem 89 (2011), 1343–1354.
83. N2 reactions revisited. Org Lett 8 (2006), 119–121.
84. N2 reactions: existence and the origin of the effect. J Org Chem 72 (2007), 5660–5667.
85. N2@C reactions. J Comput Chem 34 (2013), 1997–2005.
86. N2 reaction mechanism: dioxygen radical anion and related nucleophiles. J Am Chem Soc 122 (2000), 1740–1748.
87. Ryding, M.J., Debnárová, A., Fernández, I., Uggerud, E., Nucleophilic substitution in reactions between partially hydrated superoxide anions and alkyl halides. J Org Chem 80 (2015), 6133–6142.
88. Grant, G.H., Hinshelwood, C.N., The kinetics of reactions in solution. The interaction of potassium hydroxide and the alkyl halides in ethyl alcohol. J Chem Soc, 1933, 258–261.
89. Hughes, E.D., Shapiro, U.G., Mechanism of substitution at a saturated carbon atom. Part VII. Hydrolysis of isopropyl halides. J Chem Soc, 1937, 1177–1183.
90. Marshall, B.W., Moelwyn-Hughes, E.A., 1312. The kinetics of the reactions between the methyl halides and potassium cyanide in aqueous solution. J Chem Soc, 1965, 7119–7126.
91. Gronert, S., Fagin, A.E., Okamoto, K., Mogali, S., Pratt, L.M., Leaving group effects in gas-phase substitutions and eliminations. J Am Chem Soc 126 (2004), 12977–12983.
92. Dostrovsky, I., Hughes, E.D., Mechanism of substitution at a saturated carbon atom. Part XXVI. The role of steric hindrance. (Section A) introductory remarks, and a kinetic study of the reactions of methyl, ethyl, n-propyl, isobutyl, and neopentyl bromides with sodium ethoxide in dry ethyl alcohol. J Chem Soc, 1946, 157–161.
93. Dostrovsky, I., Hughes, E.D., Mechanism of substitution at a saturated carbon atom. Part XXVII. The role of steric hindrance. Section B. A comparison of the rates of reaction of ethyl and neopentyl bromides with inorganic iodides in acetone solution. J Chem Soc, 1946, 161–164.
94. Dostrovsky, I., Hughes, E.D., Mechanism of substitution at a saturated carbon atom. Part XXVIII. The role of steric hindrance. (Section C) a comparison of the rates of reaction of methyl, ethyl, n-propyl, isobutyl, and neopentyl bromides with aqueous ethyl alcohol. J Chem Soc, 1946, 164–165.
95. Dostrovsky, I., Hughes, E.D., Mechanism of substitution at a saturated carbon atom. Part XXIX. The role of steric hindrance. (Section D) the mechanism of the reaction of neopentyl bromide with aqueous ethyl alcohol. J Chem Soc, 1946, 166–169.
96. Dostrovsky, I., Hughes, E.D., Mechanism of substitution at a saturated carbon atom. Part XXX. The role of steric hindrance. (Section E) a comparison of the rates of reaction of methyl, ethyl, n-propyl, isobutyl, and neopentyl halides with silver nitrate in aqueous ethyl alcohol. J Chem Soc, 1946, 169–171.
97. Dostrovsky, I., Hughes, E.D., Mechanism of substitution at a saturated carbon atom. Part XXXI. The role of steric hindrance. (Section F) a comparison of the rates of reaction of methyl, ethyl, n-propyl, and neopentyl bromides with wet formic acid. J Chem Soc, 1946, 171–173.
98. Dostrovsky, I., Hughes, E.D., Ingold, C.K., Mechanism of substitution at a saturated carbon atom. Part XXXII. The role of steric hindrance. (Section G) magnitude of steric effects, range of occurrence of steric and polar effects, and place of the wagner rearrangement in nucleophilic substitution and elimination. J Chem Soc, 1946, 173–194.
99. Wislicenus, J., Über die Schätzung von Haftenergien der Halogene und des Natriums an organischen Resten. Liebigs Ann Chem 212 (1882), 239–250.
100. Krishnamurthy, S., Brown, H.C., Selective reductions. 28. The fast reaction of lithium aluminum hydride with alkyl halides in tetrahydrofuran. A reappraisal of the scope of the reaction. J Org Chem 47 (1982), 276–280.
101. De La Mare, P.B.D., Mechanism of substitution at a saturated carbon atom. Part XLV. Kinetics of the interaction of bromide ions with simple alkyl bromides in acetone. J Chem Soc, 1955, 3180–3187.
102. Ridge, D.P., Beauchamp, J.L., Reactions of strong bases with alkyl halides in the gas phase. New look at E2 base-induced elimination reactions without solvent participation. J Am Chem Soc 96 (1974), 3595–3602.
103. Lum, R.C., Grabowski, J.J., Substitution competes with elimination in a gas-phase anion-molecule reaction. J Am Chem Soc 110 (1988), 8568–8570.
104. N2 and E2 reactions of alkyl halides. J Am Chem Soc 112 (1990), 8650–8655.
105. N2 reactions and related processes. J Am Chem Soc 106 (1984), 3531–3539.
106. N2 reactions. Chem Phys Lett 196 (1992), 368–376.
107. −. J Chem Phys 105 (1996), 1959–1967.
108. N2 reactions: ethyl vs methyl reactivities and extension to higher alkyls. J Am Chem Soc 119 (1997), 5013–5019.
109. N2 reactions in the gas phase and solution. J Am Chem Soc 126 (2004), 9054–9058.
110. N2 reactions. J Org Chem 79 (2014), 867–879.
111. Isaacs, N., Physical Organic Chemistry. 2nd ed., 1995, Longman Scientific & Technical, Burnt Mill, Harlow, Essex, UK.
112. Swain, C.G., Langsdorf, W.P., Concerted displacement reactions. VI. M- and p-substituent effects as evidence for a unity of mechanism in organic halide reactions. J Am Chem Soc 73 (1951), 2813–2819.
113. Jaffé, H.H., A reëxamination of the Hammett equation. Chem Rev 53 (1953), 191–261.
114. Stein, A.R., Tencer, M., Moffatt, E.A., Dawe, R., Sweet, J., Nonlinearity of Hammett σρ correlations for benzylic systems: activation parameters and their mechanistic implications. J Org Chem 45 (1980), 3539–3540.
115. N2 reactions: identity exchange of substituted benzyl chlorides with chloride ion. J Am Chem Soc 116 (1994), 2471–2480.
116. N2 benzylic effect. J Am Chem Soc 130 (2008), 9887–9896.
117. N2 reactions with allylic substrates—trends in reactivity. Int J Mass Spectrom 265 (2007), 169–175.
118. N2 reaction. J Chem Theory Comput 2 (2006), 1220–1227.
119. Bernasconi, C.F., Mechanisms of nucleophilic aromatic and hetero-aromatic substitution. Recent developments. Chimia 34 (1980), 1–11.
120. Fernández, I., Frenking, G., Uggerud, E., Rate-determining factors in nucleophilic aromatic substitution reactions. J Org Chem 75 (2010), 2971–2980.
121. Bernasconi, C.F., Nucleophilic addition to olefins. Kinetics and mechanism. Tetrahedron 45 (1989), 4017–4090.
122. NVσ mechanistic dichotomy. J Org Chem 78 (2013), 8574–8584.
123. Ren, Y., Wolk, J.L., Hoz, S., A G2(+) level investigation of the gas-phase identity nucleophilic substitution at neutral oxygen. Int J Mass Spectrom 220 (2002), 1–10.
124. N2 reactions at neutral oxygen. Int J Mass Spectrom 225 (2003), 167–176.
125. Kobayashi, J., Kawashima, T., Chemistry of pentacoordinated anti-apicophilic phosphorus compounds. C R Chim 13 (2010), 1249–1259.
126. N2 transition states: nucleophilic substitution at α-substituted carbon and silicon centers. Int J Mass Spectrom 413 (2017), 85–91.
127. Donald, K.J., Hoffmann, R., Solid memory: structural preferences in group 2 dihalide monomers, dimers, and solids. J Am Chem Soc 128 (2006), 11236–11249.
128. Haaland, A., Tilset, M., Lewis and Kossel's legacy: structure and bonding in main-group compounds. Mingos, D.M.P., (eds.) The Chemical Bond II: 100 Years Old and Getting Stronger, 2016, Springer International Publishing, Cham, 1–70.
129. Gilheany, D.G., No d orbitals but Walsh diagrams and maybe banana bonds: chemical bonding in phosphines, phosphine oxides, and phosphonium ylides. Chem Rev 94 (1994), 1339–1374.
130. Pimentel, G.C., The bonding of trihalide and bifluoride ions by the molecular orbital method. J Chem Phys 19 (1951), 446–448.
131. Hach, R.J., Rundle, R.E., The structure of tetramethylammonium pentaiodide. J Am Chem Soc 73 (1951), 4321–4324.
132. Shaik, S., Shurki, A., Valence bond diagrams and chemical reactivity. Angew Chem Int Ed 38 (1999), 586–625.
133. Pierrefixe, S.C.A.H., Fonseca Guerra, C., Bickelhaupt, F.M., Hypervalent silicon versus carbon: ball-in-a-box model. Chem A Eur J 14 (2008), 819–828.
134. N2(Si) reactions with retention of configuration. J Phys Chem A 113 (2009), 5432–5445.
135. McClelland, R.A., Oxygen exchange in methanol in acid solutions. Transition state activity coefficients. Can J Chem 58 (1980), 393–398.
136. Bache-Andreassen, L., Uggerud, E., Theoretical models and experimental data for reactions between water with protonated alcohols. Substitution and elimination mechanisms. Chem A Eur J 5 (1999), 1917–1930.
137. Laerdahl, J.K., Uggerud, E., Nucleophilic identity substitution reactions. I. The reaction between water and protonated alcohols. Org Biomol Chem 1 (2003), 2935–2942.
138. Laerdahl, J.K., Bache-Andreassen, L., Uggerud, E., Nucleophilic identity substitution reactions. II. The reaction between ammonia and protonated amines. Org Biomol Chem 1 (2003), 2943–2950.
139. Laerdahl, J.K., Civcir, P.U., Bache-Andreassen, L., Uggerud, E., Nucleophilic identity substitution reactions. The reaction between hydrogen fluoride and protonated alkyl fluorides. Org Biomol Chem 4 (2006), 135–141.
140. Doering, W.E., Zeiss, H.H., Methanolysis of optically active hydrogen 2,4-dimethylhexyl-4-phthalate. J Am Chem Soc 75 (1953), 4733–4738.
141. More, O.F.R.A., Relationships between E2 and E1cB mechanisms of β-elimination. J Chem Soc B, 1970, 274–277.
142. Jencks, W.P., General acid-base catalysis of complex reactions in water. Chem Rev 72 (1972), 705–718.
143. Jencks, W.P., How does a reaction choose its mechanism?. Chem Soc Rev 10 (1981), 345–375.
144. N2 transition state variation by the use of more O'Ferrall plots. J Am Chem Soc 101 (1979), 3295–3300.
145. Yamashita, M., Yamamoto, Y., Akiba, K.-y., et al. Syntheses and structures of hypervalent pentacoordinate carbon and boron compounds bearing an anthracene skeleton—elucidation of hypervalent interaction based on X-ray analysis and DFT calculation. J Am Chem Soc 127 (2005), 4354–4371.
146. Akiba, K.-y., Moriyama, Y., Mizozoe, M., et al. Synthesis and characterization of stable hypervalent carbon compounds (10-C-5) bearing a 2,6-bis(p-substituted phenyloxymethyl)benzene ligand. J Am Chem Soc 127 (2005), 5893–5901.
147. +. Angew Chem Int Ed 46 (2007), 381–385.
148. Fernández, I., Uggerud, E., Frenking, G., Stable pentacoordinate carbocations: structure and bonding. Chem A Eur J 13 (2007), 8620–8626.
149. Pierrefixe, S.C.A.H., van Stralen, S.J.M., van Stralen, J.N.P., Fonseca Guerra, C., Bickelhaupt, F.M., Hypervalent carbon atom: “freezing” the SN2 transition state. Angew Chem Int Ed 48 (2009), 6469–6471.
150. Filippi, A., Speranza, M., Troposelective substitutions in microsolvated systems. J Am Chem Soc 123 (2001), 6077–6082.
151. N2 alkyl cation transfer reactions between neutral and protonated alcohols. J Phys Chem A 107 (2003), 668–675.
152. N2 reactions. Adv Phys Org Chem 41 (2006), 217–273.
153. Kohen, A., Limbach, H.-H., (eds.) Isotope Effects in Chemistry and Biology, 2005, CRC Press, Boca Raton.
154. Wolfsberg, M., Van Hook, W.A., Paneth, P., Kinetic isotope effects on chemical reactions. Isotope Effects: In the Chemical, Geological, and Bio Sciences, 2009, Springer Netherlands, Dordrecht, 313–342.
155. Wolfe, S., Kim, C.-K., Secondary H/D isotope effects in methyl-transfer reactions decrease with increasing looseness of the transition structure. J Am Chem Soc 113 (1991), 8056–8061.
156. 3Cl. J Am Chem Soc 113 (1991), 826–832.
157. Barnes, J.A., Williams, I.H., Theoretical investigation of the origin of secondary α-deuterium kinetic isotope effects. J Chem Soc Chem Commun, 1993, 1286–1287.
158. N2 transition states. J Am Chem Soc 116 (1994), 2526–2533.
159. Glad, S.S., Jensen, F., Transition state looseness and α-secondary kinetic isotope effects. J Am Chem Soc 119 (1997), 227–232.
160. 3Br. J Am Chem Soc 113 (1991), 9404–9405.
161. N2 pathways. J Am Chem Soc 113 (1991), 4009–4010.
162. 3X + Y- (X, Y = Cl, Br, I). J Am Chem Soc 117 (1995), 10726–10734.
163. N2 methyl transfer: a computational study of anionic and cationic identity reactions. J Chem Soc, Perkin Trans 2, 2002, 591–597.
164. Williams, I.H., Theoretical modeling of compression effects in enzymic methyl transfer. J Am Chem Soc 106 (1984), 7206–7212.
165. N2 methyl transfer: a computational reappraisal. J Am Chem Soc 122 (2000), 10895–10902.
166. Ruggiero, G.D., Williams, I.H., Roca, M., Moliner, V., Tuñón, I., QM/MM determination of kinetic isotope effects for COMT-catalyzed methyl transfer does not support compression hypothesis. J Am Chem Soc 126 (2004), 8634–8635.
167. Kanaan, N., Ruiz Pernia, J.J., Williams, I.H., QM/MM simulations for methyl transfer in solution and catalysed by COMT: ensemble-averaging of kinetic isotope effects. Chem Commun, 2008, 6114–6116.
168. N2 reaction of hydroxide ion with methyl iodide. The relationship between different carbon isotope effects. J Am Chem Soc 112 (1990), 6661–6668.
169. Costentin, C., Savéant, J.-M., Why are proton transfers at carbon slow? Self-exchange reactions. J Am Chem Soc 126 (2004), 14787–14795.
170. Bernasconi, C.F., Intrinsic barriers of reactions and the principle of nonperfect synchronization. Acc Chem Res 20 (1987), 301–308.
171. Bernasconi, C.F., The principle of non-perfect synchronization. Adv Phys Org Chem 27 (1992), 119–238.
172. Evans, M.G., Polanyi, M., Inertia and driving force of chemical reactions. Trans Faraday Soc 34 (1938), 11–24.
173. Evans, M.G., Warhurst, E., The activation energy of diene association reactions. Trans Faraday Soc 34 (1938), 614–624.
174. N2 transition state structure. Tetrahedron Lett 23 (1982), 5467–5470.
175. Pross, A., Shaik, S., A qualitative valence-bond approach to organic reactivity. Acc Chem Res 16 (1983), 363–370.
176. N2 reactivity patterns: a state correlation diagram model. Prog Phys Org Chem 15 (1985), 197–337.
177. Pross, A.A., General approach to organic reactivity: the configuration mixing model. Adv Phys Org Chem, 21, 1985, 99.
178. N2 reactions. J Am Chem Soc 113 (1991), 1072–1076.
179. N2 reactions. Can J Chem 70 (1992), 450–455.
180. N2 reactions. J Am Chem Soc 116 (1994), 262–273.
181. Shaik, S., Duzy, E., Bartuv, A., The quantum mechanical resonance energy of transition states. An indicator of transition state geometry and electronic structure. J Phys Chem 94 (1990), 6574–6582.
182. Shaik, S., Reddy, A.C., Transition states, avoided crossing states and valence-bond mixing: fundamental reactivity paradigms. J Chem Soc Faraday Trans 90 (1994), 1631–1642.
183. Pearson, R.G., Hard and soft acids and bases. J Am Chem Soc 85 (1963), 3533–3539.
184. Parr, R.G., Pearson, R.G., Absolute hardness: companion parameter to absolute electronegativity. J Am Chem Soc 105 (1983), 7512–7516.
185. Parr, R.G., Yang, W., Density-Functional Theory of Atoms and Molecules. 1989, Oxford University Press, Oxford.
186. Parr, R.G., Lv, S., Liu, S., Electrophilicity index. J Am Chem Soc 121 (1999), 1922–1924.
187. Arnaut, L.G., Formosinho, S.J., Understanding chemical reactivity: the case for atom, proton and methyl transfers. Chem A Eur J 14 (2008), 6578–6587.
188. N2 reaction in gas phase and solution using a DFT interpretation. J Phys Chem A 105 (2001), 591–601.
189. Arnaut, L.G., Pais, A.A.C.C., Formosinho, S.J., The intersecting-state model: a link between molecular spectroscopy and chemical reactivity. J Mol Struct 563-564 (2001), 1–17.
190. N2 reactions and their relation to molecular and solvent properties. Chem A Eur J 13 (2007), 8018–8028.
191. N2 reactions. J Chem Theory Comput 8 (2012), 3574–3585.
192. 2O. J Chem Phys 55 (1971), 1236–1244.
193. Ziegler, T., Rauk, A., On the calculation of bonding energies by the Hartree Fock Slater method. Theor Chim Acta, 46, 1977, 1.
194. N2 mechanistic spectrum and other concepts. J Comput Chem 20 (1999), 114–128.
195. 2). Chem A Eur J 9 (2003), 2173–2192.
196. N2 reactions. Chem A Eur J 15 (2009), 2166–2175.
197. van Zeist, W.-J., Bickelhaupt, F.M., The activation strain model of chemical reactivity. Org Biomol Chem 8 (2010), 3118–3127.
198. N2 reaction barriers in gas phase. J Phys Chem A 114 (2010), 5913–5918.
199. Gilbert, R.G., Smith, S.C., Theory of Unimolecular and Recombination Reactions. 1990, Blackwell Scientific, Oxford.
200. Dodd, J.A., Brauman, J.I., Marcus theory applied to reactions with double-minimum potential surfaces. J Phys Chem 90 (1986), 3559–3562.
201. Baer, T., Hase, W.L., Unimolecular Reaction Dynamics. 1996, Oxford University Press, New York.
202. 3Br: experimental evidence for nonstatistical behavior?. J Am Chem Soc 114 (1992), 10477–10482.
203. N2 nucleophilic substitution enhanced by selective mode vibrational excitation. J Am Chem Soc 111 (1989), 2349–2351.
204. N2 nucleophilic substitution. J Phys Chem 94 (1990), 2778–2788.
205. 3Cl reactive collisions. J Chem Phys 93 (1990), 7962–7980.
206. N2 nucleophilic substitution. J Phys Chem 94 (1990), 6148–6150.
207. 3Cl system. J Chem Phys 96 (1992), 8275–8287.
208. N2 reaction that avoids its deep potential energy minimum. Science, 296, 2002, 875.
209. N2 reactions. J Am Chem Soc 118 (1996), 9360–9367.
210. N2 ion-dipole complexes. J Phys Chem A 112 (2008), 10448–10452.
211. N2 reactions. J Am Chem Soc 113 (1991), 9696–9697.
212. 3Y) in the gas phase. J Am Chem Soc 116 (1994), 3875–3883.
213. Angel, L.A., Ervin, K.M., Dynamics of the gas-phase reactions of fluoride ions with chloromethane. J Phys Chem A 105 (2001), 4042–4051.
214. N2 reaction. J Am Chem Soc 124 (2002), 336–345.
215. N2 reaction. Science 276 (1997), 1536–1538.
216. -: a guided ion beam study. J Phys Chem A 101 (1997), 5969–5986.
217. N2 intermediate. J Am Chem Soc 120 (1998), 12125–12126.
218. N2 and addition-elimination reactions. J Am Chem Soc 121 (1999), 11790–11797.
219. Chabinyc, M.L., Craig, S.L., Regan, C.K., Brauman, J.I., Gas-phase ionic reactions: dynamics and mechanism of nucleophilic displacements. Science 279 (1998), 1882–1886.
220. N2 reaction. J Am Chem Soc 122 (2000), 8783–8784.
221. N2 nucleophilic substitution. Science 266 (1994), 998–1002.
222. - rate constant versus temperature, translational energy, and H(D) isotopic substitution. J Am Chem Soc 117 (1995), 9347–9356.
223. N2 nucleophilic substitution. Chem Phys 212 (1996), 247–258.
224. −. J Phys Chem A 102 (1998), 9819–9828.
225. −. J Chem Phys 106 (1997), 575–583.
226. N2 reactions. Chem Phys Lett 312 (1999), 585–590.
227. N2 reaction: influence of azimuthal rotations. J Chem Phys 109 (1998), 8200–8217.
228. −. J Chem Phys 110 (1999), 9483–9491.
229. N2 reactions. Chemphyschem 5 (2004), 600–617.
230. - from J-dependent quantum scattering calculations. Phys Chem Chem Phys 18 (2016), 19668–19675.
231. Mikosch, J., Trippel, S., Eichhorn, C., et al. Imaging nucleophilic substitution dynamics. Science, 319, 2008, 183.
232. 3I reaction. Comparison with experiment. J Phys Chem A 117 (2013), 7162–7178.
233. N2 reaction. Nat Commun, 6, 2015, 5972.
234. N2 reactions. J Phys Chem A 119 (2015), 3134–3140.
235. N2 reaction. Science 352 (2016), 32–33.
236. Bohme, D.K., Mackay, G.I., Bridging the gap between the gas phase and solution: transition in the kinetics of nucleophilic displacement reactions. J Am Chem Soc 103 (1981), 978–979.
237. 3Br at 300 K. J Am Chem Soc 105 (1983), 5509–5510.
238. 3Cl in the relative energy range 0.03-5 eV. J Am Chem Soc 107 (1985), 2812–2814.
239. Henchman, M., Hierl, P.M., Paulson, J.F., Nucleophilic displacement in the gas phase as a function of temperature, translational energy, and solvation number. Nucleophilicity, vol 215, 1987, American Chemical Society, Washington, DC, 83–101.
240. N2 reactions of fluoride with methyl halides. J Am Chem Soc 116 (1994), 3609–3610.
241. 3Br. J Phys Chem 100 (1996), 14397–14402.
242. 3Br). J Am Chem Soc 119 (1997), 577–584.
243. 3Br. J Phys Chem A 101 (1997), 4598–4601.
244. Yamataka, H., Aida, M., An ab initio MO study on the hydrolysis of methyl chloride with explicit consideration of 13 water molecules. Chem Phys Lett 289 (1998), 105–109.
245. N2 transition states. J Am Chem Soc 121 (1999), 6690–6699.
246. 2O in the gas phase, in water clusters, and in aqueous solution. Int J Mass Spectrom 182/183 (1999), 13–22.
247. N2 reactivity: acid-catalyzed hydrolysis of alcohols. J Chem Soc, Perkin Trans 2, 2001, 448–458.
248. - reaction. Molecular dynamics simulation of reaction clusters. Acta Chem Scand 53 (1999), 1043–1053.
249. N2 reactions. J Am Chem Soc 131 (2009), 16162–16170.
250. − in water. J Phys Chem A 115 (2011), 12047–12052.
251. N2 reactions of microsolvated anions. J Am Chem Soc 135 (2013), 15508–15514.
252. N2 reactions of microsolvated anions: methanol as a solvent. J Phys Chem A 118 (2014), 8060–8066.
253. N2 reaction. J Comput Chem 36 (2015), 844–852.
254. 3Cl. J Phys Chem A 104 (2000), 497–503.
255. 3Cl: a full dimensional ab initio direct dynamics study. J Phys Chem A 105 (2001), 1260–1266.
256. N2 valence-bond state correlation diagram ins aqueous solution. J Phys Chem A 112 (2008), 13157–13163.
257. Otto, R., Brox, J., Trippel, S., Stei, M., Best, T., Wester, R., Single solvent molecules can affect the dynamics of substitution reactions. Nat Chem 4 (2012), 534–538.
258. Otto, R., Xie, J., Brox, J., et al. Reaction dynamics of temperature-variable anion water clusters studied with crossed beams and by direct dynamics. Faraday Discuss 157 (2012), 41–57.
259. N2 reaction of the hydroxyl anion. J Phys Chem A 117 (2013), 8139–8144.
260. N2 reaction dynamics. Insight into the suppressed formation of solvated products. J Phys Chem Lett 7 (2016), 660–665.