Journal of the American Chemical Society
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Catalyzed by Manganese Porphyrins and Imidazole: Selection of the Best
Experimental Section, Tables S1 – S3 and Figures S1 – S12 (PDF)
Catalytic System and Nature of the Active Oxygen Species. J. Am. Chem.
Soc. 1988, 110, 8462-8470. (f) Guo, M.; Dong, H.; Li, J.; Cheng, B.;
Huang, Y.-q.; Feng, Y.-q.; Lei, A. Spectroscopic Observation of
Iodosylarene Metalloporphyrin Adducts and Manganese(V)-Oxo
Porphyrin Species in a Cytochrome P450 Analogue. Nature Commun. 2012,
3, 1190. (g) Hill, C. L.; Schardt, B. C. Alkane Activation and
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AUTHOR INFORMATION
Corresponding Author
*wwnam@ewha.ac.kr
*fukuzumi@chem.eng.osaka-u.ac.jp
Functionalization under Mild Conditions by
a
Homogeneous
Manganese(III)Porphyrin-Iodosylbenzene Oxidizing System. J. Am. Chem.
Soc. 1980, 102, 6374-6375.
Notes
The authors declare no competing financial interests.
(7) (a) Song, W. J.; Seo, M. S.; DeBeer George, S.; Ohta, T.; Song, R.;
Kang, M.-J.; Tosha, T.; Kitagawa, T.; Solomon, E. I.; Nam, W. Synthesis,
Characterization, and Reactivities of Manganese(V)-Oxo Porphyrin
Complexes. J. Am. Chem. Soc. 2007, 129, 1268-1277; (b) Jin, N.; Ibrahim,
M.; Spiro, T. G.; Groves, J. T. Trans-dioxo Manganese(V) Porphyrins. J.
Am. Chem. Soc. 2007, 129, 12416-12417.
9
ACKNOWLEDGMENT
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This work was supported by the NRF of Korea through CRI
(NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to
(8) (a) Groves, J. T.; Stern, M. K. Synthesis, Characterization, and
Reactivity of Oxomanganese(IV) Porphyrin Complexes. J. Am. Chem. Soc.
1988, 110, 8628-8638; (b) Chellaiah, A.; Yong‐Min, L.; Yoon, L. J.;
Shunichi, F.; Wonwoo, N. Hydrogen‐Atom Abstraction Reactions by
Manganese(V)– and Manganese(IV)–Oxo Porphyrin Complexes in
Aqueous Solution. Chem. - Eur. J. 2009, 15, 11482-11489; (c) Fukuzumi,
S.; Fujioka, N.; Kotani, H.; Ohkubo, K.; Lee, Y.-M.; Nam, W.
Mechanistic Insights into Hydride-Transfer and Electron-Transfer
Reactions by a Manganese(IV)−Oxo Porphyrin Complex. J. Am. Chem.
Soc. 2009, 131, 17127-17134. (d) Zhang, R.; Horner, J. H.; Newcomb, M.
Laser Flash Photolysis Generation and Kinetic Studies of
Porphyrin−Manganese−Oxo Intermediates. Rate Constants for
Oxidations Effected by Porphyrin−MnV−Oxo Species and Apparent
Disproportionation Equilibrium Constants for Porphyrin−MnIV−Oxo
Species. J. Am. Chem. Soc. 2005, 127, 6573-6582.
(9) (a) Parsell, T. H.; Behan, R. K.; Green, M. T.; Hendrich, M. P.;
Borovik, A. S. Preparation and Properties of a Monomeric MnIV−Oxo
Complex. J. Am. Chem. Soc. 2006, 128, 8728-8729; (b) Sawant, S. C.; Wu,
X.; Cho, J.; Cho, K.-B.; Kim, S. H.; Seo, M. S.; Lee, Y.-M.; Kubo, M.;
Ogura, T.; Shaik, S.; Nam, W. Water as an Oxygen Source: Synthesis,
Characterization, and Reactivity Studies of a Mononuclear Nonheme
Manganese(IV) Oxo Complex. Angew. Chem., Int. Ed. 2010, 49, 8190-8194;
(c) Wu, X.; Seo, M. S.; Davis, K. M.; Lee, Y.-M.; Chen, J.; Cho, K.-B.;
Pushkar, Y. N.; Nam, W. A Highly Reactive Mononuclear Non-Heme
Manganese(IV)–Oxo Complex That Can Activate the Strong C–H Bonds
of Alkanes. J. Am. Chem. Soc. 2011, 133, 20088-20091; (d) Leto, D. F.;
Ingram, R.; Day, V. W.; Jackson, T. A. Spectroscopic Properties and
Reactivity of a Mononuclear Oxomanganese(IV) Complex. Chem. Commun.
2013, 49, 5378-5380; (e) Barman, P.; Vardhaman, A. K.; Martin, B.;
Wörner, S. J.; Sastri, C. V.; Comba, P. Influence of Ligand Architecture
on Oxidation Reactions by High-Valent Nonheme Manganese Oxo
Complexes Using Water as a Source of Oxygen. Angew. Chem., Int. Ed.
2015, 54, 2095-2099.
W.N.)
and
Basic
Science
to
Research
Y.M.L.
Program
and
(2017R1D1A1B03029982
2017R1D1A1B03032615 to S.F.). W.N. acknowledges the use of
resonance Raman facility at IBS (IBS-R10-A1) in Korea.
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(10)
Abbreviations
used:
TDCPP,
meso-tetrakis(2,6-
dichlorophenyl)porphinato dianion; TMP, meso-tetramesitylporphinato
dianion; CSI-MS, cold spray ionization mass spectrum; EPR, electron
paramagnetic resonance; rRaman, resonance Raman; KIE, kinetic isotope
effect; CHD, 1,4-cyclohexadiene; BDE, bond dissociation energy; Bn-
TPEN, N-benzyl-N,N',N'-tris(2-pyridylmethyl)-1,2-diaminoethane.
(11) (a) Terner, J.; Palaniappan, V.; Gold, A.; Weiss, R.; Fitzgerald, M.
M.; Sullivan, A. M.; Hosten, C. M. Resonance Raman Spectroscopy of
Oxoiron(IV) Porphyrin π-Cation Radical and Oxoiron(IV) Hemes in
Peroxidase Intermediates. J. Inorg. Biochem. 2006, 100, 480-501; (b)
Nakamoto, K. Resonance Raman Spectra and Biological Significance of
High-Valent Iron(IV,V) Porphyrins. Coord. Chem. Rev. 2002, 226, 153-165;
(c) Czernuszewicz, R. S.; Su, Y. O.; Stern, M. K.; Macor, K. A.; Kim, D.;
Groves, J. T.; Spiro, T. G. Oxomanganese(IV) Porphyrins Identified by
Resonance Raman and Infrared Spectroscopy. Weak Bonds and the
Stability of the Half-filled t2g Subshell. J. Am. Chem. Soc. 1988, 110, 4158-
4165.
(12) Lei and co-workers reported that the reaction of [MnIII(TDCPP)Cl]
and iodosylarene under the conditions described in this study afforded the
formation of
a Mn(V)(O) species without detailed spectroscopic
characterization.6f However, the present work demonstrates
unambiguously that the intermediate is not a Mn(V)(O) species but a
Mn(IV)(O) species.
(13) When base was added to the solution of 1, the UV-vis spectrum of the
reaction solution indicated the formation of MnIV(O)(OH)(TMP) (Figure
S9).8a The latter species was inactive in the C-H bond activation reactions
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