10.1002/chem.202002135
Chemistry - A European Journal
FULL PAPER
In conclusion, we observed that NiIII–F complex 2 reacted with
electron rich phenols via an HAT mechanism while electron poor
phenols reacted through a stepwise PT/ET reaction mechanism.
This was supported by product and kinetic data analysis. Analysis
Gericke, M. Lovisari, D. Nelis, P. Mondal, P. Pirovano, B. Twamley, E. R.
Farquhar, A. R. McDonald, Inorg. Chem. 2019, 58, 16838-16848.
P. Mondal, P. Pirovano, A. Das, E. R. Farquhar, A. R. McDonald, J. Am.
Chem. Soc. 2018, 140, 1834-1841.
[5]
[6]
[7]
P. Pirovano, E. R. Farquhar, M. Swart, A. J. Fitzpatrick, G. G. Morgan, A.
R. McDonald, Chem. - Eur. J. 2015, 21, 3785-3790.
of kinetics/thermodynamic parameters among
a family of
analogous complexes ([NiIII(Z)(L)], Z = F, Cl, ONO2) suggested
that the basicity of the terminal ligands has a major role in
controlling the reaction mechanism. 2 reacted with 4-H-2,6-DTBP
via HAT at higher rates (one or two orders of magnitude)
compared to the analogous [NiIII(Z)(L)], a difference that was
attributed to the strong H–F bond driving the reactions.[2f, 5-6] Our
systems showed that ancillary ligands play a significant role in
tuning the reaction rates and reaction mechanism of PCET
oxidation. Our results also emphasised that high valent metal-
halides can be a potential strong oxidant and useful tools in
understanding the mechanism of different bio-inspired chemical
oxidation reactions.
J. W. Darcy, B. Koronkiewicz, G. A. Parada, J. M. Mayer, Acc. Chem.
Res. 2018, 51, 2391-2399.
[8]
[9]
V. F. DeTuri, K. M. Ervin, J. Phys. Chem. A 1999, 103, 6911-6920.
P. Mondal, M. Lovisari, B. Twamley, A. R. McDonald, Angew. Chem. Int.
Ed. 2020. DOI: 10.1002/anie.202004639.
[10] aN. L. Zabik, C. N. Virca, T. M. McCormick, S. Martic-Milne, J. Phys.
Chem. B 2016, 120, 8914-8924; bM. Lovisari, A. R. McDonald, Inorg.
Chem. 2020, 59, 3659-3665.
[11] T. Kurahashi, A. Kikuchi, Y. Shiro, M. Hada, H. Fujii, Inorg. Chem. 2010,
49, 6664-6672.
[12] aJ. S. Wright, E. R. Johnson, G. A. DiLabio, J. Am. Chem. Soc. 2001,
123, 1173-1183; bG. Grampp, S. Landgraf, C. Mureşanu, Electrochim.
Acta 2004, 49, 537-544; cJ. Jover, R. Bosque, J. Sales, Qsar Com. Sci.
2007, 26, 385-397.
[13] aP. Barman, A. K. Vardhaman, B. Martin, S. J. Wörner, C. V. Sastri, P.
Comba, Angew. Chem. Int. Ed. 2015, 54, 2095-2099; bM.-C. Kafentzi, M.
Orio, M. Réglier, S. Yao, U. Kuhlmann, P. Hildebrandt, M. Driess, A. J.
Simaan, K. Ray, Dalton Trans. 2016, 45, 15994-16000.
Experimental Section
See supporting information file for experimental details.
[14] T. Gadosy, D. Shukla, L. Johnston, J. Phys. Chem. A 1999, 103, 8834-
8839.
[15] J. P. Roth, S. Lovell, J. M. Mayer, J. Am. Chem. Soc. 2000, 122, 5486-
5498.
Keywords: High valent oxidants • PCET • oxidation catalysis •
phenol oxidation • ligand tuning
[16] aK. A. Gardner, L. L. Kuehnert, J. M. Mayer, Inorg. Chem. 1997, 36,
2069-2078; bC. R. Goldsmith, R. T. Jonas, T. D. P. Stack, J. Am. Chem.
Soc. 2002, 124, 83-96; cJ. R. Bryant, J. M. Mayer, J. Am. Chem. Soc.
2003, 125, 10351-10361; dG. Yin, A. M. Danby, D. Kitko, J. D. Carter, W.
M. Scheper, D. H. Busch, J. Am. Chem. Soc. 2008, 130, 16245-16253;
eE. J. Klinker, S. Shaik, H. Hirao, L. Que Jr, Angew. Chem. Int. Ed. 2009,
Acknowledgements
This publication has emanated from research supported by the
f
48, 1291-1295; D. Wang, M. Zhang, P. Bꢀhlmann, L. Que Jr, J. Am.
European
Research
Council
(ERC-2015-STG-678202).
Chem. Soc. 2010, 132, 7638-7644; gD. Dhar, W. B. Tolman, J. Am. Chem.
Soc. 2015, 137, 1322-1329; hD. Mandal, S. Shaik, J. Am. Chem. Soc.
2016, 138, 2094-2097.
Research in the McDonald lab is supported in part by a research
grant from Science Foundation Ireland (SFI/15/RS-URF/3307).
[17] aL. R. Mahoney, M. DaRooge, J. Am. Chem. Soc. 1970, 92, 890-899; bD.
A. Pratt, G. A. DiLabio, P. Mulder, K. Ingold, Acc. Chem. Res. 2004, 37,
334-340; cJ. Cho, S. Jeon, S. A. Wilson, L. V. Liu, E. A. Kang, J. J.
Braymer, M. H. Lim, B. Hedman, K. O. Hodgson, J. S. Valentine, Nature
2011, 478, 502-505; dM. S. Seo, N. H. Kim, K.-B. Cho, J. E. So, S. K.
Park, M. Clémancey, R. Garcia-Serres, J.-M. Latour, S. Shaik, W. Nam,
Chem. Sci. 2011, 2, 1039-1045; eJ. Cho, J. Woo, J. E. Han, M. Kubo, T.
[1]
[2]
aJ. M. Mayer, Annu. Rev. Phys. Chem. 2004, 55, 363-390; bM. H. V.
Huynh, T. J. Meyer, Chem. Rev. 2007, 107, 5004-5064; cJ. M. Mayer,
Acc. Chem. Res. 2010, 44, 36-46; dS. Hammes-Schiffer, A. A.
Stuchebrukhov, Chem. Rev. 2010, 110, 6939-6960; eJ. J. Warren, T. A.
Tronic, J. M. Mayer, Chem. Rev. 2010, 110, 6961-7001.
aT. H. Parsell, M.-Y. Yang, A. Borovik, J. Am. Chem. Soc. 2009, 131,
2762-2763; bA. Borovik, Chem. Soc. Rev. 2011, 40, 1870-1874; cP. J.
Donoghue, J. Tehranchi, C. J. Cramer, R. Sarangi, E. I. Solomon, W. B.
Tolman, J. Am. Chem. Soc. 2011, 133, 17602-17605; dY. Morimoto, J.
Park, T. Suenobu, Y.-M. Lee, W. Nam, S. Fukuzumi, Inorg. Chem. 2012,
51, 10025-10036; eD. Usharani, D. C. Lacy, A. Borovik, S. Shaik, J. Am.
f
Ogura, W. Nam, Chem. Sci. 2011, 2, 2057-2062; P. Leeladee, High-
valent manganese and iron corrolazines: Effect of Lewis acids, atom and
group transfer reactions, The Johns Hopkins University, 2012.
[18] R. A. Marcus, N. Sutin, Biochimica et Biophysica Acta -Reviews on
Bioenergetics 1985, 811, 265-322.
[19] aJ. B. Guttenplan, S. G. Cohen, J. Am. Chem. Soc. 1972, 94, 4040-4042;
bP. J. Wagner, H. M. Lam, J. Am. Chem. Soc. 1980, 102, 4167-4172; cM.
Ram, J. T. Hupp, J. Phys. Chem. A 1990, 94, 2378-2380; dS. C.
Weatherly, I. V. Yang, H. H. Thorp, J. Am. Chem. Soc. 2001, 123, 1236-
1237; eI. Garcia-Bosch, R. E. Cowley, D. E. Díaz, R. L. Peterson, E. I.
Solomon, K. D. Karlin, J. Am. Chem. Soc. 2017, 139, 3186-3195.
[20] S. Kundu, E. Miceli, E. R. Farquhar, K. Ray, Dalton Trans. 2014, 43,
4264-4267.
f
Chem. Soc. 2013, 135, 17090-17104; P. Pirovano, E. R. Farquhar, M.
Swart, A. R. McDonald, J. Am. Chem. Soc. 2016, 138, 14362-14370.
aD. T. Yiu, M. F. Lee, W. W. Lam, T.-C. Lau, Inorg. Chem. 2003, 42,
1225-1232; bD. E. Lansky, D. P. Goldberg, Inorg. Chem. 2006, 45, 5119-
5125; cT. Tano, Y. Okubo, A. Kunishita, M. Kubo, H. Sugimoto, N. Fujieda,
T. Ogura, S. Itoh, Inorg. Chem. 2013, 52, 10431-10437; dJ. Xie, L. Ma,
W. W. Lam, K.-C. Lau, T.-C. Lau, Dalton Trans. 2016, 45, 70-73; eD.
Dhar, G. M. Yee, T. F. Markle, J. M. Mayer, W. B. Tolman, Chem. Sci.
2017, 8, 1075-1085; fJ. P. T. Zaragoza, M. A. Siegler, D. P. Goldberg, J.
Am. Chem. Soc. 2018, 140, 4380-4390; gS. V. Lymar, M. Z. Ertem, D. E.
Polyansky, Dalton Trans. 2018, 47, 15917-15928.
aT. Osako, K. Ohkubo, M. Taki, Y. Tachi, S. Fukuzumi, S. Itoh, J. Am.
Chem. Soc. 2003, 125, 11027-11033; bR. Gupta, A. Borovik, J. Am.
Chem. Soc. 2003, 125, 13234-13242; cJ. Y. Lee, R. L. Peterson, K.
Ohkubo, I. Garcia-Bosch, R. A. Himes, J. Woertink, C. D. Moore, E. I.
Solomon, S. Fukuzumi, K. D. Karlin, J. Am. Chem. Soc. 2014, 136, 9925-
9937; dJ. Jung, S. Kim, Y. M. Lee, W. Nam, S. Fukuzumi, Angew. Chem.
Int. Ed. 2016, 55, 7450-7454; eW. D. Bailey, D. Dhar, A. C. Cramblitt, W.
[3]
[21] C. McManus, P. Mondal, M. Lovisari, B. Twamley, A. R. McDonald, Inorg.
Chem. 2019, 58, 4515-4523.
[22] aE. L. Lebeau, R. A. Binstead, T. J. Meyer, J. Am. Chem. Soc. 2001, 123,
10535-10544; bE.-S. El-Samanody, K. D. Demadis, T. J. Meyer, P. S.
White, Inorg. Chem. 2001, 40, 3677-3686; cJ. M. Mayer, J. Phys. Chem.
Lett. 2011, 2, 1481-1489.
[4]
[23] J. Riveranevares, J. Wyman, D. Vonminden, N. Lacy, M. Chabinyc, A.
Fratini, D. Macys, Environ. Toxicol. Chem. 1995, 14, 251-256.
f
B. Tolman, J. Am. Chem. Soc. 2019, 141, 5470-5480; D. Unjaroen, R.
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