10.1002/anie.202005091
Angewandte Chemie International Edition
COMMUNICATION
see Figure S19).[16] To the best of our knowledge, the present
study reports the first example of using a metal-iodosylbenzene
adduct as a terminal oxidant for the generation of high-valent
metal-oxo species.
[7] a) M. Sankaralingam, Y.-M. Lee, W. Nam, S. Fukuzumi, Coord. Chem.
Rev. 2018, 365, 41; b) B. Kim, D. Jeong, T. Ohta, J. Cho, Commun. Chem.
2019, 2, 81; c) S. H. Bae, X.-X. Li, M. S. Seo, Y.-M. Lee, S. Fukuzumi, W.
Nam, J. Am. Chem. Soc. 2019, 141, 7675; d) M. Sankaralingam, Y.-M.
Lee, S. H. Jeon, M. S. Seo, K.-B. Cho, W. Nam, Chem. Commun. 2018,
54, 1209; e) J. 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, E. I.
Solomon, W. Nam, Nature 2011, 478, 502.
In conclusion, we have reported for the first time the X-ray
crystal structure of a mononuclear nonheme Co(III)-OIPh adduct,
[CoIII(TQA)(OIPh)(OH)]2+, which exhibits an amphoteric reactivity
in electrophilic and nucleophilic reactions in the presence of a
small amount of proton. We have also shown that metal-
iodosylarene complexes can be used as a terminal oxidant for the
generation of metal-oxo species. In future studies, we will focus
on elucidating the detailed mechanisms of metal-iodosylarene
species in oxidation reactions as well as in the OAT reaction for
the formation of metal-oxo species. The effects of proton and
metal ions on the reactivity of metal-iodosylarene species is
currently under investigation in this laboratory.[17]
[8] a) J. M. Bollinger, Jr., C. Krebs, Curr. Opin. Chem. Biol. 2007, 11, 151; b)
S. Fukuzumi, Y.-M. Lee, W. Nam, Dalton Trans. 2019, 48, 9469; c) H. Noh,
J. Cho, Coord. Chem. Rev. 2019, 382, 126.
[9] a) W. D. Bailey, N. L. Gagnon, C. E. Elwell, A. C. Cramblitt, C. J. Bouchey,
W. B. Tolman, Inorg. Chem. 2019, 58, 4706; b) A. R. Corcos, O.
Villanueva, R. C. Walroth, S. K. Sharma, J. Bacsa, K. M. Lancaster, C. E.
MacBeth, J. F. Berry, J. Am. Chem. Soc. 2016, 138, 1796; c) S. Hong, K.
D. Sutherlin, J. Park, E. Kwon, M. A. Siegler, E. I. Solomon, W. Nam, Nat.
Commun. 2014, 5, 5440; d) P. Pirovano, A. M. Magherusan, C. McGlynn,
A. Ure, A. Lynes, A. R. McDonald, Angew. Chem. Int. Ed. 2014, 53, 5946.
[10] a) V. V. Zhdankin, J. D. Protasiewicz, Coord. Chem. Rev. 2014, 275, 54;
b) A. Yoshimura, V. V. Zhdankin, Chem. Rev. 2016, 116, 3328.
[11] a) M. Guo, Y.-M. Lee, M. S. Seo, Y.-J. Kwon, X.-X. Li, T. Ohta, W.-S. Kim,
R. Sarangi, S. Fukuzumi, W. Nam, Inorg. Chem. 2018, 57, 10232; b) Y.
Kang, X.-X. Li, K.-B. Cho, W. Sun, C. Xia, W. Nam, Y. Wang, J. Am. Chem.
Soc. 2017, 139, 7444; c) B. Wang, Y.-M. Lee, M. S. Seo, W. Nam, Angew.
Chem. Int. Ed. 2015, 54, 11740; d) S. Hong, B. Wang, M. S. Seo, Y.-M.
Lee, M. J. Kim, H. R. Kim, T. Ogura, R. Garcia-Serres, M. Clémancey, J.-
M. Latour, W. Nam, Angew. Chem. Int. Ed. 2014, 53, 6388; e) P. Leeladee,
D. P. Goldberg, Inorg. Chem. 2010, 49, 3083; f) S. H. Wang, B. S.
Mandimutsira, R. Todd, B. Ramdhanie, J. P. Fox, D. P. Goldberg, J. Am.
Chem. Soc. 2004, 126, 18; g) K. P. Bryliakov, E. P. Talsi, Angew. Chem.
Int. Ed. 2004, 43, 5228; h) W. Nam, Y. O. Ryu, W. J. Song, J. Biol. Inorg.
Chem. 2004, 9, 654; i) J. A. Smegal, C. L. Hill, J. Am. Chem. Soc. 1983,
105, 2920.
Acknowledgements
This work was supported by the NRF of Korea through CRI (NRF-
2012R1A3A2048842 to W.N.), Basic Science Research Program
(2017R1D1A1B03029982 to Y.M.L., 2017R1D1A1B03032615 to
S.F., and 2019R1I1A1A01055822 to M.S.S.) and the NSF of USA
(CHE-1900380 and CHE-1854854 to J.S.).
Keywords: Cobalt(III)-Iodosylbenzene Adduct • Nucleophilic
Reactivity • Electrophilic Reactivity • Amphoteric Reactivity •
Aldehyde Deformylation Reaction
[12] a) C. Wang, T. Kurahashi, H. Fujii, Angew. Chem. Int. Ed. 2012, 51, 7809;
b) A. Lennartson, C. J. McKenzie, Angew. Chem. Int. Ed. 2012, 51, 6767;
c) C. Wang, T. Kurahashi, K. Inomata, M. Hada, H. Fujii, Inorg. Chem.
2013, 52, 9557; d) C. Wegeberg, C. G. Frankæ r, C. J. McKenzie, Dalton
Trans. 2016, 45, 17714; e) D. Jeong, T. Ohta, J. Cho, J. Am. Chem. Soc.
2018, 140, 16037.
[1] a) W. Nam, Acc. Chem. Res. 2007, 40, 465 and references therein; b) L.
Que, J. Biol. Inorg. Chem. 2017, 22, 171 and references therein.
[2] a) M. Guo, T. Corona, K. Ray, W. Nam, ACS Cent. Sci. 2019, 5, 13; b) K.
D. Dubey, S. Shaik, Acc. Chem. Res. 2019, 52, 389; c) X. Huang, J. T.
Groves, Chem. Rev. 2018, 118, 2491; d) R. A. Baglia, J. P. T. Zaragoza,
D. P. Goldberg, Chem. Rev. 2017, 117, 13320; e) W. Nam, Acc. Chem.
Res. 2015, 48, 2415.
[13] E. A. Hill, M. L. Kelty, A. S. Filatov, J. S. Anderson, Chem. Sci. 2018, 9,
4493.
[14] S. Kim, C. Saracini, M. A. Siegler, N. Drichko, K. D. Karlin, Inorg. Chem.
2012, 51, 12603.
[3] a) W. Nam, Y.-M. Lee, S. Fukuzumi, Acc. Chem. Res. 2014, 47, 1146; b)
S. A. Cook, A. S. Borovik, Acc. Chem. Res. 2015, 48, 2407; c) M. Puri, L.
Que, Jr., Acc. Chem. Res. 2015, 48, 2443; d) S. Hong, Y.-M. Lee, K. Ray,
W. Nam, Coord. Chem. Rev. 2017, 334, 25; e) J. J. D. Sacramento, D. P.
Goldberg, Acc. Chem. Res. 2018, 51, 2641; f) Y. Liu, T.-C. Lau, J. Am.
Chem. Soc. 2019, 141, 3755.
[15] Y.-R. Luo, Handbook of Bond Dissociation Energies in Organic
Compounds; CRC Press: New York, 2002.
[16] J.-U. Rohde, J.-H. In, M. H. Lim, W. W. Brennessel, M. R. Bukowski, A.
Stubna, E. Münck, W. Nam, L. Que, Jr., Science 2003, 299, 1037.
[17] The effects of Lewis and Brønsted acids on the reactivities of metal-
oxygen intermediates have been highlighted recently: (a) S. Bang, Y.-M.
Lee, S. Hong, K.-B. Cho, Y. Nishida, M. S. Seo, R. Sarangi, S. Fukuzumi,
W. Nam, Nat. Chem. 2014, 6, 934; b) S. Fukuzumi, K. Ohkubo, Y.-M. Lee,
W. Nam, Chem. Eur. J. 2015, 21, 17548; c) J. Chen, H. Yoon, Y.-M. Lee,
M. S. Seo, R. Sarangi, S. Fukuzumi, W. Nam, Chem. Sci. 2015, 6, 3624;
d) S. Hong, Y.-M. Lee, M. Sankaralingam, A. K. Vardhaman, Y. J. Park,
K.-B. Cho, T. Ogura, R. Sarangi, S. Fukuzumi, W. Nam, J. Am. Chem.
Soc. 2016, 138, 8523; e) S. H. Bae, Y.-M. Lee, S. Fukuzumi, W. Nam,
Angew. Chem. Int. Ed. 2017, 56, 801; f) T. Devi, Y.-M. Lee, W. Nam, S.
Fukuzumi, J. Am. Chem. Soc. 2018, 140, 8372.
[4] a) R. Trammell, K. Rajabimoghadam, I. Garcia-Bosch, Chem. Rev. 2019,
119, 2954; b) S. M. Adam, G. B. Wijeratne, P. J. Rogler, D. E. Diaz, D. A.
Quist, J. J. Liu, K. D. Karlin, Chem. Rev. 2018, 118, 10840; c) C. E. Elwell,
N. L. Gagnon, B. D. Neisen, D. Dhar, A. D. Spaeth, G. M. Yee, W. B.
Tolman, Chem. Rev. 2017, 117, 2059; d) D. A. Quist, D. E. Diaz, J. J. Liu,
K. D. Karlin, J. Biol. Inorg. Chem. 2017, 22, 253.
[5] J. Cho, R. Sarangi, W. Nam, Acc. Chem. Res. 2012, 45, 1321.
[6] a) P. Barman, P. Upadhyay, A. S. Faponle, J. Kumar, S. S. Nag, D. Kumar,
C. V. Sastri, S. P. de Visser, Angew. Chem. Int. Ed. 2016, 55, 11091; b)
P. Barman, F. G. C. Reinhard, U. K. Bagha, D. Kumar, C. V. Sastri, S. P.
de Visser, Angew. Chem. Int. Ed. 2019, 58, 10639.
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