The Journal of Physical Chemistry A
Article
respectively. From the slopes and intercepts of the linear plots,
(8) Nishida, Y.; Lee, Y.-M.; Nam, W.; Fukuzumi, S. Autocatalytic
Formation of an Iron(IV)−Oxo Complex via Scandium Iron−Promoted
Radical Chain Autoxidation of an Iron(II) Complex with Dioxygen and
Tetraphenylborate. J. Am. Chem. Soc. 2014, 136, 8042−8049.
the k /k and k /k values were obtained as 53 and 7,
H
−et
et
2
respectively.
(9) Shen, D.; Miao, C.; Wang, S.; Xia, C.; Sun, W. Efficient Benzylic
CONCLUSIONS
Photocatalytic oxidation of AcrH by O with (P)Mn (1 and 2)
in PhCN occurs to produce AcrO as the sole oxidation
product. The kinetic and laser flash photolysis measurements
revealed the photocatalytic mechanism, as shown in Scheme 1,
■
and Aliphatic C−H Oxidation with Selectivity for Methylenic Sites
Catalyzed by a Bioinspired Manganese Complex. Org. Lett. 2014, 16,
III
2
2
1
(
108−1111.
10) Sorokin, A. B. Phthalocyanine Metal Complexes in Catalysis.
Chem. Rev. 2013, 113, 8152−8191.
III
where electron transfer from the excited state ([(P)Mn ]*
(11) Fukuzumi, S.; Kishi, T.; Kotani, H.; Lee, Y.-M.; Nam, W. Highly
Efficient Photocatalytic Oxygenation Reactions Using Water as an
Oxygen Source. Nat. Chem. 2011, 3, 38−41.
7
(
[
T )) to O occurs to produce the superoxo complex
1
2
IV
•−
(P)Mn (O2 )], which oxidizes AcrH2 to AcrO via
IV
•−
hydrogen-atom transfer from AcrH to [(P)Mn (O )] and
(12) Paria, S.; Chatterjee, S.; Paine, T. K. Reactivity of an Iron−
Oxygen Oxidant Generated upon Oxidative Decarboxylation of
Biomimetic Iron(II) α-Hydroxy Acid Complexes. Inorg. Chem. 2014,
2
2
V
formation of (P)Mn (O). The photocatalytic reactivity of
III
(
[
(
P)Mn agrees with the rate constants of electron transfer from
III
7
III
5
3, 2810−2821.
(13) Company, A.; Sabenya, G.; Gonzal
Clemancey, M.; Blondin, G.; Jasniewski, A. J.; Puri, M.; Browne, W. R.;
(P)Mn ]* ( T ) to O in the order (TMP)Mn (OH) >
1 2
III III
́ ́ ́
ez-Bejar, M.; Gomez, L.;
TBP Cz)Mn > (TPFPP)Mn (CH COO). The present study
8
3
́
paves the way for development of new photocatalytic oxidation of
Latour, J.-M.; et al. Triggering the Generation of an Iron(IV)−Oxo
substrates by O using manganese porphyrins.
2
II
Compound and Its Reactivity toward Sulfides by Ru Photocatalysis. J.
Am. Chem. Soc. 2014, 136, 4624−4633.
ASSOCIATED CONTENT
Supporting Information
Kinetic data (Figures S1, S2, and S3), femtosecond laser flash
photolysis measurements (Figure S4), and phosphorescence
■
(
̈
14) Li, F.; Van Heuvelen, K. M.; Meier, K. K.; Munck, E.; Que, L.,
*
S
3+
Jr. Sc -Triggered Oxoiron(IV) Formation from O and Its Non-Heme
2
3+
3+
Iron(II) Precursor via a Sc −Peroxo−Fe Intermediate. J. Am. Chem.
Soc. 2013, 135, 10198−10121.
(15) Kim, S. O.; Sastri, C. V.; Seo, M. S.; Kim, J.; Nam, W. Dioxygen
Activation and Catalytic Aerobic Oxidation by a Mononuclear
Nonheme Iron(II) Complex. J. Am. Chem. Soc. 2005, 127, 4178−4179.
(16) Lee, Y.-M.; Hong, S.; Morimoto, Y.; Shin, W.; Fukuzumi, S.;
Nam, W. Dioxygen Activation by a Non-Heme Iron(II) Complex:
Formation of an Iron(IV)−Oxo Complex via C−H Activation by a
Putative Iron(III)−Superoxo Species. J. Am. Chem. Soc. 2010, 132,
AUTHOR INFORMATION
Notes
■
*
*
1
(
0668−10670.
17) Hong, S.; Lee, Y.-M.; Shin, W.; Fukuzumi, S.; Nam, W.
The authors declare no competing financial interest.
Dioxygen Activation by Mononuclear Nonheme Iron(II) Complexes
Generates Iron−Oxygen Intermediates in the Presence of an NADH
Analogue and Proton. J. Am. Chem. Soc. 2009, 131, 13910−13911.
ACKNOWLEDGMENTS
■
(
18) O’Reilly, M. E.; Del Castillo, T. J.; Falkowski, J. M.;
This work was supported by an ALCA project from the Japan
Science and Technology Agency (JST), Japan to S.F., Grants-
in-Aid (Nos. 26620154 and 26288037 to K.O.) from the
Ministry of Education, Culture, Sports, Science, and Technol-
ogy (MEXT), Japan, the NSF (CHE0909587 and CHE121386
to D.P.G.), and the NIH (GM101153 to D.P.G)
Ramachandran, V.; Pati, M.; Correia, M. C.; Abboud, K. A.; Dalal,
N. S.; Richardson, D. E.; Veige, A. S. Autocatalytic O Cleavage by an
2
OCO3 Trianionic Pincer Cr Complex: Isolation and Character-
−
III
IV
ization of the Autocatalytic Intermediate [Cr ] (μ-O) Dimer. J. Am.
2
Chem. Soc. 2011, 133, 13661−13673.
(19) McEvoy, J. P.; Brudvig, G. W. Water-Splitting Chemistry of
Photosystem II. Chem. Rev. 2006, 106, 4455−4483.
(20) Umena, Y.; Kawakami, K.; Shen, J. R.; Kamiya, N. Crystal
Structure of Oxygen-Evolving Photosystem II at a Resolution of 1.9 Å.
Nature 2011, 473, 55−60.
REFERENCES
■
(
1) Rittle, J.; Green, M. T. Cytochrome P450 Compound I: Capture,
Characterization, and C−H Bond Activation Kinetics. Science 2010,
30, 933−937.
2) Metal−oxo and Metal−Peroxo Species in Catalytic Oxidations;
Meunier, B., Ed.; Springer-Verlag: Berlin, Germany, 2000.
3) Cytochrome P450: Structure, Mechanism, and Biochemistry, 3rd ed.;
Ortiz de Montellano, P. R., Ed.; Kluwer Academic/Plenum Publishers:
New York, 2005.
4) Hrycay, E. G.; Bandiera, S. M. The Monooxygenase, Peroxidase,
and Peroxygenase Properties of Cytochrome P450. Arch. Biochem.
3
(
(21) Pecoraro, V. L.; Baldwin, M. J.; Caudle, M. T.; Hsieh, W.-Y.;
Law, N. A. A Proposal for Water Oxidation in Photosystem II. Pure
Appl. Chem. 1998, 70, 925−929.
(
(22) 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.
(
(23) Arunkumar, C.; Lee, Y.-M.; Lee, J. Y.; Fukuzumi, S.; Nam, W.
Biophys. 2012, 522, 71−89.
5) Betley, T. A.; Wu, Q.; Voorhis, T. V.; Nocera, D. G. Electronic
Hydrogen-Atom Abstraction Reactions by Manganese(V)− and
Manganese(IV)−Oxo Porphyrin Complexes in Aqueous Solution.
Chem.Eur. J. 2009, 15, 11482−11489.
(
Design Criteria for O−O Bond Formation via Metal−Oxo Complexes.
Inorg. Chem. 2008, 47, 1849−1861.
(24) Lee, J. Y.; Lee, Y.-M.; Kotani, H.; Nam, W.; Fukuzumi, S. High-
(
6) Mullins, C. S.; Pecoraro, V. L. Reflections on Small Molecule
Valent Manganese(V)−Oxo Porphyrin Complexes in Hydride Trans-
fer Reactions. Chem. Commun. 2009, 704−706.
Manganese Models that Seek to Mimic Photosynthetic Water
Oxidation Chemistry. Coord. Chem. Rev. 2008, 252, 416−443.
7) Hong, S.; Lee, Y.-M.; Shin, W.; Fukuzumi, S.; Nam, W. Dioxygen
(25) Prokop, K. A.; de Visser, S. P.; Goldberg, D. P. Unprecedented
(
Activation by Mononuclear Nonheme Iron(II) Complexes Generates
Iron−Oxygen Intermediates in the Presence of an NADH Analogue
and Proton. J. Am. Chem. Soc. 2009, 131, 13910−13911.
Rate Enhancements of Hydrogen-Atom Transfer to a Manganese(V)−
Oxo Corrolazine Complex. Angew. Chem. 2010, 122, 5217−5221;
Angew. Chem., Int. Ed. 2010, 49, 5091−5095.
6
228
dx.doi.org/10.1021/jp505860f | J. Phys. Chem. A 2014, 118, 6223−6229