Journal of the American Chemical Society
Page 4 of 5
Chem. Soc. 2018, 140, 4380. (e) Sankaralingam, M.; Lee, Y.-M.; Nam, W.;
Fukuzumi, S. Coord. Chem. Rev. 2018, 365, 41. (f) Wang, Y.; Sheng, J.; Shi,
S.; Zhu, D.; Yin, G. J. Phys. Chem. C 2012, 116, 13231.
1
2
3
4
5
6
7
8
(1) (a) Boyington, J. C.; Gaffney, B. J.; Amzel, L. M. Science 1993, 260, 1482.
(b) Minor, W.; Steczko, J.; Stec, B.; Otwinowski, Z.; Bolin, J. T.; Walter, R. ;
Axelrod, B. Biochemistry 1996, 35, 10687. (c) Skrzypczak-Jankun, E.; Bross,
R. A.; Carroll, R. T.; Dunham, W. R.; Funk, M. O. Jr. J. Am. Chem. Soc.
2001, 123, 10814. (d) Haeggström, J. Z.; Funk, C. D. Chem. Rev. 2011, 111,
5866. (e) Mitra, S.; Bartlett, S. G.; Newcomer, M. E. Biochemistry 2015, 54,
6333. (f) Kalms, J.; Banthiya, S.; Yoga, E. G.; Hamberg, M.; Holzhutter, H.-
G.; Kuhn, H.; Scheerer, P. Biochim. Biophys. Acta 2017, 1862, 463.
(2) (a) Glickman, M. H.; Klinman, J. P. Biochemistry 1995, 34, 14077. (b)
Rickert, K. W.; Klinman, J. P. Biochemistry 1999, 38, 12218. (c) Meyer, M.
P.; Tomchick, D. R.; Klinman, J. P. Proc. Natl. Acad. Sci. U. S. A. 2008, 105,
1146. (d) Klinman, J. P. Biochemistry 2013, 52, 2068. (e) Sharma, S. C.;
Klinman, J. P. Biochemistry, 2015, 54, 5447. (f) Offenbacher, A. R.; Hu, S.;
Poss, E. M.; Carr, C. A. M.; Scouras, A. D.; Prigozhin, D. M.; Iavarone, A.
T.; Palla, A.; Alber, T.; Fraser, J. S.; Klinman, J. P. ACS Cent. Sci. 2017, 3,
570. (g) Klinman, J. P.; Offenbacher, A. R.; Hu, S. J. Am. Chem. Soc. 2017,
139, 18409.
(3) (a) Hatcher, E.; Soudackov, A. V.; Hammes-Schiffer, S. J. Am. Chem. Soc.
2007, 129, 187. (b) Edwards, S. J.; Soudackov, A. V.; Hammes-Schiffer, S.
J. Phys. Chem. B 2010, 114, 6653. (c) Soudackov, A. V.; Hammes-Schiffer,
S. J. Phys. Chem. Lett. 2014, 5, 3274. (d) Li, P.; Soudackov, A. V.; Hammes-
Schiffer, S. J. Am. Chem. Soc. 2018, 140, 3068.
(4) (a) Su, C.; Sahlin, M.; Oliw, E. H. J. Biol. Chem. 2000, 275, 18830. (b)
Truhlar, D. G. J. Phys. Org. Chem. 2010, 23, 660. (c) Mavri, J.; Liu, H.; Ols-
son, M. H.; Warshel, A. J. Phys. Chem. B 2008, 112, 5950. (d) Barroso, M.;
Arnaut, L. G.; Formosinho, S. J. J. Phys. Org. Chem. 2008, 21, 659. (e)
Phatak, P.; Venderley, J.; Debrota, J.; Li, J.; Iyengar, S. S. J. Phys. Chem. B
2015, 119, 9532. (f) Salna, B.; Benabbas, A.; Russo, D.; Champion, P. M. J.
Phys. Chem. B 2017, 121, 6869. (g) Lehnert, N.; Solomon, E. I. J. Biol. In-
org. Chem. 2003, 8, 294.
(5) (a) Fukuzumi, S. Helv. Chim. Acta 2006, 89, 2425. (b) Warren, J. J.; Tronic,
T. A.; Mayer, J. M. Chem. Rev. 2010, 110, 6961. (c) Dempsey, J. L.; Winkler,
J. R.; Gray, H. B. Chem. Rev. 2010, 110, 7024. (d) Weinberg, D. R.;
Gagliardi, C. J.; Hull, J. F.; Murphy, C. F.; Kent, C. A.; Westlake, B. C.; Paul,
A.; Ess, D. H.; McCafferty, D. G.; Meyer, T. J. Chem. Rev. 2012, 112, 4016.
(e) Migliore, A.; Polizzi, N. F.; Therien, M. J.; Beratan, D. N. Chem. Rev.
2014, 114, 3381. (f) Layfield, J. P.; Hammes-Schiffer, S. Chem. Rev. 2014,
114, 3466. (g) Porter, T. R.; Mayer, J. M. Chem. Sci. 2014, 5, 372. (h) Ham-
mes-Schiffer, S. J. Am. Chem. Soc. 2015, 137, 8860.
(6) (a) Goldsmith, C. R.; Stack, T. D. P. Inorg. Chem. 2006, 45, 6048. (b)
Ching, W.-M.; Zhou, A.; Klein, J. E. M. N.; Fan, R.; Knizia, G.; Cramer, C.
J.; Guo, Y.; Que, L., Jr. Inorg. Chem. 2017, 56, 11129. (c) Gao, H.; Groves,
J. T. J. Am. Chem. Soc. 2017, 139, 3938. (d) Pirovano, P.; McDonald, A. R.
Eur. J. Inorg. Chem. 2018, 547.
(7) (a) Goldsmith, C. R.; Cole, A. P.; Stack, T. D. P. J. Am. Chem. Soc. 2005,
127, 9904. (b) Coggins, M. K.; Brines, L. M.; Kovacs, J. A. Inorg. Chem.
2013, 52, 12383. (c) Mallick, D.; Shaik, S. ACS Catal. 2016, 6, 2877.
(8) (a) Wijeratne, G. B.; Corzine, B.; Day, V. W.; Jackson, T. A. Inorg. Chem.
2014, 53, 7622. (b) Rice, D. B.; Wijeratne, G. B.; Burr, A. D.; Parham, J. D.;
Day, V. W.; Jackson, T. A. Inorg. Chem. 2016, 55, 8110.
(9) (a) Jonas, R. T.; Stack, T. D. P. J. Am. Chem. Soc. 1997, 119, 8566. (b)
Goldsmith, C. R.; Jonas, R. T.; Stack, T. D. P. J. Am. Chem. Soc. 2002, 124,
83. (c) Wijeratne, G. B.; Day, V. W.; Jackson, T. A. Dalton Trans. 2015, 44,
3295.
(11) (a) Mei, F.; Ou, C.; Wu, G.; Cao, L.; Han, F.; Meng, X.; Li, J.; Li, D.; Liao,
Z. Dalton Trans. 2010, 39, 4267. (b) Wu, G.; Mei, F.; Gao, Q.; Han, F.; Lan,
S.; Zhang, J.; Li, D. Dalton Trans. 2011, 40, 6433. (c) Chang, K.-C.; Huang,
C.-J.; Chang, Y.-H.; Wu, Z.-H.; Kuo, T.-S.; Hsu, H.-F. Inorg. Chem. 2016,
55, 566.
(12) Sankaralingam, M.; Jeon, S. H.; Lee, Y.-M.; Seo, M. S.; Ohkubo, K.; Fuku-
zumi, S.; Nam, W. Dalton Trans. 2016, 45, 376.
(13) No signal due to 1 was observed in the parallel mode EPR measurements
probably because of the large zero-field splitting that causes broadening of
the anticipated signal with parallel microwave polarization beyond detec-
tion. 2 has also been reported to give no observable signal in the parallel
mode EPR measurements (see ref 8a).
(14) Muckerman, J. T.; Skone, J. H.; Ning, M.; Wasada-Tsutsui, Y. Biochim. Bi-
ophys. Acta 2013, 1827, 882.
(15) The BDE value of 2 is smaller than that of 2,4-di-tert-butylphenol (81.85
kcal mol–1); see Yiu, D. T. Y.; Lee, M. F. W.; Lam, W. W. Y.; Lau, T.-C. Inorg.
Chem. 2003, 42, 1225. This is consistent with the fact that 2 exhibited no
reactivity towards 2,4-di-tert-butylphenol.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(16) This indicates that the BDE of 1 is larger than that of 2, although the deter-
mination of the BDE of 1 has yet to be made because of the instability of the
+
MnII(OH3 ) complex.
(17) The deuterated phenol derivative (-OD) was produced by adding D2O to
an MeCN solution of the phenol derivative (-OH). The H/D exchange
1
with D2O was confirmed by H NMR (Figure S6 in SI). The KIE values
were confirmed to the same with different concentrations of D2O (Figure
S5 in SI). D2O may also exchange D with 1 (or 2). However, the KIE results
from the O–H vs O–D bond cleavage rather than the addition of proton or
deuteron to the OH (OD) or OH2 (OD2) ligand.
(18) Park, J.; Morimoto, Y.; Lee, Y.-M.; You, Y.; Nam, W.; Fukuzumi, S. Inorg.
Chem. 2011, 50, 11612.
(19) The rate constant of HAT from xanthene to 1 is smaller than that of 2,4-di-
tert-butylphenol despite the smaller BDE of xanthene (75.5 kcal mol–1)
than that of 2,4-di-tert-butylphenol, because the cleavage of the C–H bond
requires more reorganization as compared with that of the O–H bond; see:
Lockwood, M. A.; Blubaugh, T. J.; Collier, A. M.; Lovell, S.; Mayer, J. M.
Angew. Chem., Int. Ed. 1999, 38, 225. Thus, 1 exhibited no reactivity to-
ward dihydroanthracene (BDE = 78 kcal mol–1).
(20) Devi, T.; Lee, Y.-M.; Nam, W.; Fukuzumi, S. J. Am. Chem. Soc. 2018, 140,
8372.
(21) (a) Lee, Y.-M.; Kotani, H.; Suenobu, T.; Nam, W.; Fukuzumi, S. J. Am.
Chem. Soc. 2008, 130, 434. (b) Fukuzumi, S. Coord. Chem. Rev. 2013, 257,
1564.
(22) The higher reduction potential of 1 than 2, results from the binding of pro-
ton to the hydroxo ligand to produce the H2O ligand, which makes 1 more
electron deficient as compared with 2. Similar positive shifts of the one-elec-
tron reduction potentials have been observed by binding of redox-inactive
metal ions and Brønsted acids to manganese(IV)-oxo complexes; see: (a)
Yoon, H.; Lee, Y.-M.; Wu, X.; Cho, K.-B.; Sarangi, R.; Nam, W.; Fukuzumi,
S.; J. Am. Chem. Soc. 2013, 135, 9186. (b) Chen, J.; Yoon, H.; Lee, Y.-M.;
Seo, M. S.; Sarangi, R.; Fukuzumi, S.; Nam, W. Chem. Sci. 2015, 6, 3624.
(23) Marcus, R. A. Annu. Rev. Phys. Chem. 1964, 15, 155.
(24) The larger value may result from the elongation of the O–H bond upon
the ET oxidation; see: Schrauben, J. N.; Cattaneo, M.; Day, T. C.; Tender-
holt, A. L.; Mayer, J. M. J. Am. Chem. Soc. 2012, 134, 16635.
(10) (a) Wang, Y.; Shi, S.; Zhu, D.; Yin, G. Dalton Trans. 2012, 41, 2612. (b) Yin,
G. Acc. Chem. Res. 2013, 46, 483. (c) Chen, Z.; Yin, G. Chem. Soc. Rev.
2015, 44, 1083. (d) Zaragoza, J. P. T.; Siegler, M. A.; Goldberg, D. P. J. Am.
ACS Paragon Plus Environment