Journal of the American Chemical Society
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MnV(O) corrolazine was more active in OAT than the valence
tautomer MnIV(O-LA) cation radical corrolazine (LA = Zn2+,
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CONCLUSION
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Mn(IV)-hydroxo corrole radical cation has been prepared by
the reaction of Mn(V)-oxo corrole with TFA. While the valence
tautomer (tpfc+•)MnIV(OH) is more stable than (tpfc)MnV(O)
(days versus hours in open air and moisture), it exhibits
enhanced reactivity in ET reactions, a rate enhancement by
approximately 5 orders of magnitude (Scheme 7). In HAT
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Scheme 7
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(29) Gross, Z.; Galili, N.; Simkhovich, L.; Saltsman, I.; Botoshansky,
reactions with 2,4-(tBu)2 phenol both valence tautomers exhibit
comparable rate constants and identical KIE. While (tpfc)-
MnV(O) is capable of undergoing OAT with PhSMe with a
second-order rate constant of 0.70 M−1 s−1, (tpfc+•)MnIV(OH)
does not react at all with PhSMe (Scheme 7). These differences
illustrate the importance of valence and electronic structure on
redox reactions of high-valent porphyrinoid complexes.
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
M.; Blaser, D.; Boese, R.; Goldberg, I. Org. Lett. 1999, 1, 599.
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2000, 39, 4045.
UV−vis spectra, cyclic voltammetry, EPR, NMR, and
̈
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16971.
(32) Liu, H.-Y.; Lai, T.-S.; Yeung, L.-L.; Chang, C. K. Org. Lett. 2003,
AUTHOR INFORMATION
Corresponding Author
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5, 617.
(33) Simkhovich, L.; Mahammed, A.; Goldberg, I.; Gross, Z. Chem. -
Eur. J. 2001, 7, 1041.
(34) Meier-Callahan, A. E.; Di Bilio, A. J.; Simkhovich, L.;
Mahammed, A.; Goldberg, I.; Gray, H. B.; Gross, Z. Inorg. Chem.
2001, 40, 6788.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This research was supported by a grant from the U.S. National
Science Foundation (NSF grant no. CHE-1463900).
■
(35) Wang, C.; Kurahashi, T.; Inomata, K.; Hada, M.; Fujii, H. Inorg.
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