-
1
-
-
36949063535
-
-
Blois, M. S. Nature 1958, 181, 1199-1200.
-
(1958)
Nature
, vol.181
, pp. 1199-1200
-
-
Blois, M.S.1
-
3
-
-
31844441727
-
-
Mulder, P.; Litwinienko, G.; Lin, S.; MacLean, P. D.; Barclay, L. R. C.; Ingold, K. U. Chem. Res. Toxicol. 2006, 19, 79-85.
-
(2006)
Chem. Res. Toxicol
, vol.19
, pp. 79-85
-
-
Mulder, P.1
Litwinienko, G.2
Lin, S.3
MacLean, P.D.4
Barclay, L.R.C.5
Ingold, K.U.6
-
4
-
-
44949206009
-
-
The transfer of a hydrogen atom formally involves the transfer of an electron and a proton. When electron and proton are transferred to the same center in the same step, we generally speak of HAT mechanism. Very recently, however, DFT theoretical calculations5-7 have shown that quite energetically different situations can arise depending on whether the same or different sets of orbitals are involved in the transfer of the proton and the electron. In the former case, the mechanism continues to be designated as HAT; in the latter case, the process is described as a proton coupled electron transfer (PCET) or a concerted proton electron transfer CPET, Theoretical calculations8 have also shown that both HAT and CPET pathways are possible for the reaction of dpph• with phenols. It should, however, be noted that Huynh and Meyer9 have expressed some reservation on the distinction discussed above. According to these authors, the C
-
9 have expressed some reservation on the distinction discussed above. According to these authors, the CPET terminology should be strictly reserved to when proton and electron are transferred to orbitals located in well separated sites.
-
-
-
-
5
-
-
0037130656
-
-
Mayer, J. M.; Hrovat, D. A.; Thomas, J. L.; Borden, W. T. J. Am. Chem. Soc. 2002, 124, 11142-11147.
-
(2002)
J. Am. Chem. Soc
, vol.124
, pp. 11142-11147
-
-
Mayer, J.M.1
Hrovat, D.A.2
Thomas, J.L.3
Borden, W.T.4
-
10
-
-
1842505047
-
-
Foti, M. C.; Daquino, C.; Geraci, C. J. Org. Chem. 2004, 69, 2309-2314.
-
(2004)
J. Org. Chem
, vol.69
, pp. 2309-2314
-
-
Foti, M.C.1
Daquino, C.2
Geraci, C.3
-
14
-
-
0035857407
-
-
(a) Wright, J. S.; Johnson, E. R.; Di Labio, G. A. J. Am. Chem. Soc. 2001, 123, 1173-1183.
-
(2001)
J. Am. Chem. Soc
, vol.123
, pp. 1173-1183
-
-
Wright, J.S.1
Johnson, E.R.2
Di Labio, G.A.3
-
15
-
-
84962429291
-
-
(b) Leopoldini, M.; Marino, T.; Russo, N.; Toscano, M. J. Phys. Chem. A 2004, 108, 4916-4922.
-
(2004)
J. Phys. Chem. A
, vol.108
, pp. 4916-4922
-
-
Leopoldini, M.1
Marino, T.2
Russo, N.3
Toscano, M.4
-
16
-
-
1642502300
-
-
(c) Leopoldini, M.; Pitarch, I. P.; Russo, N.; Toscano, M. J. Phys. Chem. A 2004, 108, 92-96.
-
(2004)
J. Phys. Chem. A
, vol.108
, pp. 92-96
-
-
Leopoldini, M.1
Pitarch, I.P.2
Russo, N.3
Toscano, M.4
-
17
-
-
20044365411
-
-
Nakanishi, I.; Kawashima, T.; Ohkubo, K.; Kanazawa, H.; Inami, K.; Mochizuchi, M.; Fukuhara, K.; Okuda, H.; Ozawa, T.; Itoh, S.; Fukuzumi, S.; Ikota, N. Org. Biomol. Chem. 2005, 3, 626-629.
-
(2005)
Org. Biomol. Chem
, vol.3
, pp. 626-629
-
-
Nakanishi, I.1
Kawashima, T.2
Ohkubo, K.3
Kanazawa, H.4
Inami, K.5
Mochizuchi, M.6
Fukuhara, K.7
Okuda, H.8
Ozawa, T.9
Itoh, S.10
Fukuzumi, S.11
Ikota, N.12
-
18
-
-
0001345994
-
-
Mahoney, L. R.; Mendenhall, G. D.; Ingold, K. U. J. Am. Chem. Soc. 1973, 95, 8610-8614.
-
(1973)
J. Am. Chem. Soc
, vol.95
, pp. 8610-8614
-
-
Mahoney, L.R.1
Mendenhall, G.D.2
Ingold, K.U.3
-
19
-
-
35948933950
-
-
Fukuzumi, S.; Tokuda, Y.; Chiba, Y.; Greci, L.; Carloni, P.; Damiani, E. J. Chem. Soc., Chem. Commun. 1993, 1575-1577.
-
(1993)
J. Chem. Soc., Chem. Commun
, pp. 1575-1577
-
-
Fukuzumi, S.1
Tokuda, Y.2
Chiba, Y.3
Greci, L.4
Carloni, P.5
Damiani, E.6
-
20
-
-
0030768537
-
-
Rüchardt, C.; Gerst, M.; Ebenoch, J. Angew. Chem., Int. Ed. Engl. 1997, 36, 1406.
-
(1997)
Angew. Chem., Int. Ed. Engl
, vol.36
, pp. 1406
-
-
Rüchardt, C.1
Gerst, M.2
Ebenoch, J.3
-
21
-
-
0037153284
-
-
For other application of this criterion, see
-
For other application of this criterion, see: Nakanishi, I.; Miyazaki, K.; Shimada, T.; Ohkubo, K.; Urano, S.; Ikota, N.; Ozawa, T.; Fukuzumi, S.; Fukuhara, K. J. Phys. Chem. A 2002, 106, 11123-11126.
-
(2002)
J. Phys. Chem. A
, vol.106
, pp. 11123-11126
-
-
Nakanishi, I.1
Miyazaki, K.2
Shimada, T.3
Ohkubo, K.4
Urano, S.5
Ikota, N.6
Ozawa, T.7
Fukuzumi, S.8
Fukuhara, K.9
-
22
-
-
0036025629
-
-
2+ ref 20
-
2+ (ref 20)
-
(2002)
J. Chem. Soc., Perkin Trans. 2
, pp. 1520-1524
-
-
Nakanishi, I.1
Fukuhara, K.2
Shimada, T.3
Ohkubo, K.4
Iizuka, Y.5
Inami, K.6
Mochizuchi, M.7
Urano, S.8
Itoh, S.9
Miyata, N.10
Fukuzumi, S.11
-
23
-
-
0042350771
-
-
and references therein
-
Fukuzumi, S.; Shimoosako, K.; Suenobu, T.; Watanabe, Y. J. Am. Chem. Soc. 2003, 125, 9074-9082, and references therein.
-
(2003)
J. Am. Chem. Soc
, vol.125
, pp. 9074-9082
-
-
Fukuzumi, S.1
Shimoosako, K.2
Suenobu, T.3
Watanabe, Y.4
-
24
-
-
44949258603
-
-
17
-
17
-
-
-
-
25
-
-
44949246923
-
-
In a more recent study, however, the reaction of N-Me-AcrH 2 with dpph• has been assumed to take place by a HAT mechanism.3
-
3
-
-
-
-
26
-
-
0033593262
-
-
Dombrowski, G. W.; Dinnocenzo, J. P.; Farid, S.; Goodman, J. L.; Gould, I. R. J. Org. Chem. 1999, 64, 427-431.
-
(1999)
J. Org. Chem
, vol.64
, pp. 427-431
-
-
Dombrowski, G.W.1
Dinnocenzo, J.P.2
Farid, S.3
Goodman, J.L.4
Gould, I.R.5
-
29
-
-
0028947612
-
-
Karki, S. B.; Dinnocenzo, J. P.; Jones, J. P.; Korzekwa, K. R. J. Am. Chem. Soc. 1995, 117, 3657-3664.
-
(1995)
J. Am. Chem. Soc
, vol.117
, pp. 3657-3664
-
-
Karki, S.B.1
Dinnocenzo, J.P.2
Jones, J.P.3
Korzekwa, K.R.4
-
30
-
-
33845278203
-
-
Wayner, D. D. M.; McPhee, D. J.; Griller, D. J. Am. Chem. Soc. 1988, 110, 132-137.
-
(1988)
J. Am. Chem. Soc
, vol.110
, pp. 132-137
-
-
Wayner, D.D.M.1
McPhee, D.J.2
Griller, D.3
-
31
-
-
44949110664
-
-
28
-
28
-
-
-
-
32
-
-
0000729874
-
-
Valgimigli, L.; Ingold, K. U.; Lusztyk, J. J. Org. Chem. 1996, 61, 7947-7950.
-
(1996)
J. Org. Chem
, vol.61
, pp. 7947-7950
-
-
Valgimigli, L.1
Ingold, K.U.2
Lusztyk, J.3
-
33
-
-
44949182388
-
-
The correlation was much worse using the Hammett σ constants
-
The correlation was much worse using the Hammett σ constants.
-
-
-
-
34
-
-
20844463434
-
-
Baciocchi, E.; Bietti, M.; Gerini, M. F.; Lanzalunga, O. J. Org. Chem. 2005, 70, 5144-5149.
-
(2005)
J. Org. Chem
, vol.70
, pp. 5144-5149
-
-
Baciocchi, E.1
Bietti, M.2
Gerini, M.F.3
Lanzalunga, O.4
-
35
-
-
0004032955
-
-
Kochi, J. K, Ed, John Wiley & Sons: New York, Chapter 7
-
Russell, G. A. In Free Radicals; Kochi, J. K., Ed.; John Wiley & Sons: New York, 1973; Vol. 1, Chapter 7.
-
(1973)
Free Radicals
, vol.1
-
-
Russell, G.A.1
-
36
-
-
44949261627
-
-
20
-
20
-
-
-
-
37
-
-
44949113831
-
-
25
-
25
-
-
-
-
38
-
-
44949220737
-
-
35
-
35
-
-
-
-
40
-
-
44949181388
-
-
It should be noted, however, that if deprotonation of the radical cation, eq 2 in Scheme 1, is carried out exclusively by dpph, no retarding effect by dpph- is expected in a preequilibrium ET mechanism. However, it is probable that substantial deprotonation by the solvent is also occurring in view of the extremely small concentration of dpph- at the equilibrium
-
- at the equilibrium.
-
-
-
-
41
-
-
33644779089
-
-
Kitaguchi, H.; Ohkubo, K.; Ogo, S.; Fukuzumi, S. J. Phys. Chem. A 2006, 110, 1718-1725.
-
(2006)
J. Phys. Chem. A
, vol.110
, pp. 1718-1725
-
-
Kitaguchi, H.1
Ohkubo, K.2
Ogo, S.3
Fukuzumi, S.4
-
42
-
-
0347852563
-
-
Fukuzumi, S.; Koumitsu, S.; Hironaka, K.; Tanaka, T. J. Am. Chem. Soc. 1987, 109, 305.
-
(1987)
J. Am. Chem. Soc
, vol.109
, pp. 305
-
-
Fukuzumi, S.1
Koumitsu, S.2
Hironaka, K.3
Tanaka, T.4
-
43
-
-
34547193702
-
-
Koner, A. L.; Pischel, U.; Nau, W. M. Org. Lett. 2007, 9, 2899-2902.
-
(2007)
Org. Lett
, vol.9
, pp. 2899-2902
-
-
Koner, A.L.1
Pischel, U.2
Nau, W.M.3
-
44
-
-
44949251376
-
-
This appears to be a general outcome for reactions involving hydrogen transfer from a C-H bond. These processes are generally slightly faster in solvents of lower polarity even when the transition state has a polar character. Entropy compensation effects are probably at play.41
-
41
-
-
-
-
45
-
-
40749101057
-
-
DeZutter, C. B.; Horner, J. H.; Newcomb, M. J. Phys. Chem. A 2008, 112, 1891-1896.
-
(2008)
J. Phys. Chem. A
, vol.112
, pp. 1891-1896
-
-
DeZutter, C.B.1
Horner, J.H.2
Newcomb, M.3
-
46
-
-
44949232761
-
-
In the HAT transition state, a partial positive charge should develop on the methyl carbon, which should make it more difficult to rationalize the ρ value observed
-
In the HAT transition state, a partial positive charge should develop on the methyl carbon, which should make it more difficult to rationalize the ρ value observed.
-
-
-
-
47
-
-
44949144550
-
-
2+ concentration and a reaction order of ca 0.3 was calculated (see Figure S6 in the Supporting Information).
-
2+ concentration and a reaction order of ca 0.3 was calculated (see Figure S6 in the Supporting Information).
-
-
-
|