Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(V)-oxo species
作者： Rui Zhang , Eric Vanover , Weilong Luo , Martin Newcomb
DOI: 10.1039/C4DT00649F
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摘要: Photo-disproportionation of a bis-porphyrin-diruthenium(IV) μ-oxo dimer gave porphyrin-ruthenium(III) species and putative porphyrin-ruthenium(V)-oxo that can be detected studied in real time via laser flash photolysis methods. As determined by its spectral kinetic behavior, the same oxo transient was also formed N-oxide adduct. Second-order rate constants for reactions with several substrates at 22 °C were determined; representative values kox = 6.6 × 103 M−1 s−1 diphenylmethanol, 2.5 styrene, 1.8 cyclohexene. The reacted 5–6 orders magnitude faster than corresponding trans-dioxoruthenium(VI) porphyrins, obtained this work similar to those corrole-iron(V)-oxo derivative. high reactivity photochemically generated ruthenium-oxo comparison other porphyrin-metal-oxo intermediates suggests it is true ruthenium(V)-oxo species.
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sci-hub.se 参考文章(48)
J. P. Collman, C. E. Barnes, P. J. Brothers, T. J. Collins, T. Ozawa, J. C. Gallucci, James A. Ibers, Oxidation of ruthenium(II) and ruthenium(III) porphyrins. Crystal structures of .mu.-oxo-bis[(p-methylphenoxo)(meso-tetraphenylporphyrinato)ruthenium(IV)] and ethoxo(meso-tetraphenylporphyrinato)(ethanol)ruthenium(III)-bisethanol Journal of the American Chemical Society. ,vol. 106, pp. 5151- 5163 ,(1984) , 10.1021/JA00330A020
Martin Newcomb, Rui Zhang, R. Esala P. Chandrasena, James A. Halgrimson, John H. Horner, Thomas M. Makris, Stephen G. Sligar, Cytochrome P450 Compound I Journal of the American Chemical Society. ,vol. 128, pp. 4580- 4581 ,(2006) , 10.1021/JA060048Y
Miquel Costas, Mark P. Mehn, Michael P. Jensen, Lawrence Que, Dioxygen Activation at Mononuclear Nonheme Iron Active Sites: Enzymes, Models, and Intermediates Chemical Reviews. ,vol. 104, pp. 939- 986 ,(2004) , 10.1021/CR020628N
F. T. de Oliveira, A. Chanda, D. Banerjee, X. Shan, S. Mondal, L. Que, E. L. Bominaar, E. Munck, T. J. Collins, Chemical and Spectroscopic Evidence for an FeV-Oxo Complex Science. ,vol. 315, pp. 835- 838 ,(2007) , 10.1126/SCIENCE.1133417
Rui Zhang, Wing-Yiu Yu, Kwok-Yin Wong, Chi-Ming Che, Highly Efficient Asymmetric Epoxidation of Alkenes with aD4-Symmetric Chiral Dichlororuthenium(IV) Porphyrin Catalyst The Journal of Organic Chemistry. ,vol. 66, pp. 8145- 8153 ,(2001) , 10.1021/JO010329I
Zeev Gross, Santiago Ini, Dual Role of Pyridine N-Oxides in Ruthenium Porphyrin-Catalyzed Asymmetric Epoxidation of Olefins Inorganic Chemistry. ,vol. 38, pp. 1446- 1449 ,(1999) , 10.1021/IC981021L
Masanori Sono, Mark P. Roach, Eric D. Coulter, John H. Dawson, Heme-Containing Oxygenases Chemical Reviews. ,vol. 96, pp. 2841- 2888 ,(1996) , 10.1021/CR9500500
Robert M. Richman, Mark W. Peterson, Photodisproportionation of (. mu. -oxo)bis((tetraphenylporphinato)iron(III)) Journal of the American Chemical Society. ,vol. 104, pp. 5795- 5796 ,(1982) , 10.1021/JA00385A045
Rui Zhang, Martin Newcomb, Laser Flash Photolysis Formation and Direct Kinetic Studies of Manganese(V)-Oxo Porphyrin Intermediates Journal of the American Chemical Society. ,vol. 125, pp. 12418- 12419 ,(2003) , 10.1021/JA0377448
John T. Groves, Jinbo Lee, Sudhakar S. Marla, Detection and Characterization of an Oxomanganese(V) Porphyrin Complex by Rapid-Mixing Stopped-Flow Spectrophotometry Journal of the American Chemical Society. ,vol. 119, pp. 6269- 6273 ,(1997) , 10.1021/JA962605U