Oxygen Atom Transfer Reaction of Manganese-oxo Corrole toward Dimethyl Sulfide: a Density Functional Study

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摘要 The effects of axial ligand on the oxygen atom transfer (OAT) reaction from 5,10,15-tris(pentafluorophenyl) corrole ((tpfc)MnVO) to dimethyl sulfide (DMS) have been investigated by density functional theory (DFT) calculations. Imidazole (Im), 4-methylimidazole (4-MI) and pyridine (Py) were selected as the axial ligands. The results revealed that the axial ligand can form coordinate bond with (tpfc)MnVO in the transition state (TS) of the OAT reaction. The axial coordination favored charge transferring from (tpfc)MnVO to DMS, and weakened the Mn≡O bond in both singlet and triplet states. Furthermore, axial coordination can reduce the energy barrier of neutral (tpfc)MnVO from 23.62 kJ·mol-1 to less than 3 kJ·mol-1 in the triplet state, which is significantly lower than in the singlet state. This makes (tpfc)MnVO tend to direct the OAT reaction via triplet state pathway. On the other hand, the energy barriers of [(tpfc)MnVIO]+ species from disproportionation pathway increased from 1.26 to 33.95 kJ·mol-1 in a doublet state. This suggests axial ligands were conducive for direct (tpfc)MnVO OAT reaction pathway.

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	徐艳
	徐志广
	章小慧
	陈华彬
	许旋
	刘海洋

关键词 ： corrole, manganese-oxo, oxygen atom transfer reaction, density functional theory, axial ligand

Abstract：The effects of axial ligand on the oxygen atom transfer (OAT) reaction from 5,10,15-tris(pentafluorophenyl) corrole ((tpfc)MnVO) to dimethyl sulfide (DMS) have been investigated by density functional theory (DFT) calculations. Imidazole (Im), 4-methylimidazole (4-MI) and pyridine (Py) were selected as the axial ligands. The results revealed that the axial ligand can form coordinate bond with (tpfc)MnVO in the transition state (TS) of the OAT reaction. The axial coordination favored charge transferring from (tpfc)MnVO to DMS, and weakened the Mn≡O bond in both singlet and triplet states. Furthermore, axial coordination can reduce the energy barrier of neutral (tpfc)MnVO from 23.62 kJ·mol-1 to less than 3 kJ·mol-1 in the triplet state, which is significantly lower than in the singlet state. This makes (tpfc)MnVO tend to direct the OAT reaction via triplet state pathway. On the other hand, the energy barriers of [(tpfc)MnVIO]+ species from disproportionation pathway increased from 1.26 to 33.95 kJ·mol-1 in a doublet state. This suggests axial ligands were conducive for direct (tpfc)MnVO OAT reaction pathway.

Key words： corrole manganese-oxo oxygen atom transfer reaction density functional theory axial ligand

收稿日期: 2019-03-05 出版日期: 2019-10-30

基金资助:This project was supported by the National Natural Science Foundation of China (21275057, 21671068) and Natural Science Foundation of Guangdong Province (S2012010008763, 2017A050506048)

通讯作者: chzgxu@scnu.edu.cn E-mail: chzgxu@scnu.edu.cn

引用本文:

徐艳;徐志广;章小慧;陈华彬;许旋;刘海洋. Oxygen Atom Transfer Reaction of Manganese-oxo Corrole toward Dimethyl Sulfide: a Density Functional Study[J]. 结构化学, 2019, 38(11): 1857-1866.
XU Yan;XU Zhi-Guang;ZHANG Xiao-Hui;CHEN Hua-Bin;XU Xuan;LIU Hai-Yang. Oxygen Atom Transfer Reaction of Manganese-oxo Corrole toward Dimethyl Sulfide: a Density Functional Study. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2019, 38(11): 1857-1866.

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http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2019/V38/I11/1857

REFERENCES
(1) Rebelo, S. L. H.; Pereira, M. M.; Simões, M. M. Q.; Neves, M. G. P. M.; Cavaleiro, J. A. S. Mechanistic studies on metalloporphyrin epoxidation reactions with hydrogen peroxide: evidence for two active oxidative species. J. Catal. 2005, 234, 7687.
(2) Zhang, R.; Newcomb, M. Laser flash photolysis formation and direct kinetic studies of manganese(V)-oxo porphyrin intermediates. J. Am. Chem. Soc. 2003, 125, 1241812419.
(3) Strassner, T.; Houk, K. N. Predictions of geometries and multiplicities of the manganese-oxo intermediates in the Jacobsen epoxidation. Org. Lett. 1999, 1, 419421.
(4) Gross, Z.; Galili, N.; Saltsman, I. The first direct synthesis of corroles from pyrrole. Angew. Chem. Int. Ed. 1999, 38, 14271429.
(5) Gross, Z.; Simkhovich, L.; Galili, N. First catalysis by corrole metal complexes: epoxidation, hydroxylation, and cyclopropanation. Chem. Commun. 1999, 30, 599600.
(6) Zhu, C.; Liang, J. X. Theoretical insight into the interaction between gallium di-corrole dyes and iodine in dye-sensitized solar cells (DSCs). J. Power. Sources 2015, 283, 343350.
(7) Liu, H. Y.; Mahmood, M. H. R.; Qiu, S. X.; Chang, C. K. Recent developments in manganese corrole chemistry. Coord. Chem. Rev. 2013, 257, 13061333.
(8) Aviv-Harel, I.; Gross, Z. Coordination chemistry of corroles with focus on main group elements. Coord. Chem. Rev. 2011, 255, 717736.
(9) Yang, W. C.; Mo, T. T.; Lin, Z. T.; Zeng, S. Y.; Fang, Y. Q.; Jiang, T.; Shi, L. Synthesis of mono-hydroxyl corrole manganese(III) complex and its interaction with DNA. Chin. J. Synth. Chem. 2017, 25, 6064.
(10) Yang, M.; Wang, H. H.; Liu, H. Y. Copper corrole catalyzed cross-dehydrogenative coupling of C(sp3)-H substrate with carboxylic acids. Chem. Res. Appl. 2018, 30, 357362.
(11) Fang, Y. Q.; Zeng, S. Y.; Yu, H. J.; Wang, C. B.; Li, X.; Yin, W.; Shi, L. Synthesis of a novel phenothiazine-corrole manganese(III) complex and its ctatalytic activity on oxidative cleavage of DNA. Chin. J. Synth. Chem. 2018, 26, 332336.
(12) Liu, H. Y.; Yam, F.; Xie, Y. T.; Li, X. Y.; Chang, C. K. A bulky bis-pocket manganese(V)-oxo corrole complex: observation of oxygen atom transfer between triply bonded MnV≡O and alkene. J. Am. Chem. Soc. 2009, 131, 1289012891.
(13) Zaragoza, J. P. T.; Baglia, R. A.; Siegler, M. A.; Goldberg, D. P. Strong inhibition of O-atom transfer reactivity for MnIV(O)(p-radical-cation)(lewis acid) versusMnV(O) porphyrinoid complexes. J. Am. Chem. Soc. 2015, 137, 65316540.
(14) Collman, J. P.; Zeng, L.; Decreau, R. A. Multiple active oxidants in competitive epoxidations catalyzed by porphyrins and corroles. Chem. Commun. 2004, 9, 29742975.
(15) Liu, H. Y.; Lai, T. S.; Yeung, L. L.; Chang, C. K. First synthesis of perfluorinated corrole and its MnO complex. Org. Lett. 2003, 5, 617620.
(16) Zhang, R.; Harischandra, D. N.; Newcomb, M. Laser flash photolysis generation and kinetic studies of corrole-manganese(V)-oxo intermediates. Chem. Eur. J. 2005, 11, 57135720.
(17) Zhang, R.; Newcomb, M. Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time. Acc. Chem. Res. 2008, 41, 468477.
(18) Zhu, C.; Liang, J.; Wang, B.; Zhu, J.; Cao, Z. X. Significant effect of spin flip on the oxygen atom transfer reaction from (oxo)manganese(V) corroles to thioanisole: insights from density functional calculations. Phys. Chem. Chem. Phys. 2012, 14, 1280012806.
(19) Gross, Z.; Golubkov, G.; Simkhovich, L. Epoxidation catalysis by a manganese corrole and isolation of an oxomanganese(V) corrole we acknowledge the partial support of this research by \"the fund for the promotion of research at the technion\". Angew. Chem. Int. Ed. Engl. 2010, 39, 40454047.
(20) Kumar, A.; Goldberg, I.; Botoshansky, M.; Buchman, Y.; Gross, Z. Oxygen atom transfer reactions from isolated (oxo)manganese(V) corroles to sulfides. J. Am. Chem. Soc. 2010, 132, 1523315245.
(21) Ng, N. C.; Mahmood, M. H. R.; Yam, F.; Liu, H. Y.; Yeung, L. L.; Chang, C. K. Appended corrole manganese complexes: catalysis and axial-ligand effect. Chin. Chem. 2014, 25, 571574.
(22) Liu, H. Y.; Zhou, H.; Liu, L. Y.; Ying, X.; Jiang, H. F.; Chang, C. K. The effect of axial ligand on the reactivity of oxomanganese(V) corrole. Chem. Lett. 2007, 36, 274275.
(23) Xu, Y.; Zhang, X. H.; Xu, Z. G.; Chen, H. B.; Liu, H. Y. Effects of substituents and anionic ligands for axial coordination of manganese(V)-oxo corrole complex. J. South. Chin. Norm. Univ.: Nat. Sci. Ed. 2019, 51, 2834.
(24) Neu, H. M.; Yang, T.; Baglia, R. A.; Yosca, T. H.; Green, M. T.; Quesne, M. G.; de Visser, S. P.; Goldberg, D. P. Oxygen-atom transfer reactivity of axially ligated Mn(V)-oxo complexes: evidence for enhanced electrophilic and nucleophilic pathways. J. Am. Chem. Soc. 2014, 136, 1384513852.
(25) Neu, H. M.; Quesne, M. G.; Yang, T.; Prokop-Prigge, K. A.; Lancaster, K. M.; Donohoe, J.; DeBeer, S.; de Visser, S. P.; Goldberg, D. P. Dramatic influence of an anionic donor on the oxygen-atom transfer reactivity of a MnV-oxo complex. Chem. Eur. J. 2014, 20, 1458414588.
(26) Gonzalez, C.; Schlegel, H. B. An improved algorithm for reaction path following. J. Chem. Phys. 1989, 90, 21542161.
(27) Gonzalez, C.; Schlegel, H. B. Reaction path following in mass-weighted internal coordinates. J. Phys. Chem. 1990, 94, 55235527.
(28) Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993, 98, 56485652.
(29) He, J.; Xu, Z. G.; Xu, X.; Gong, L. Z.; Mahmood, M. H. R.; Liu, H. Y. Reactivity of (oxo)manganese(V) corroles in one-electron redox state: insights from conceptual DFT and transition state calculations. J. Porphyr. Phthalocya. 2013, 17, 11961203.
(30) He, J.; Xu, Z. G.; Zeng, Y. X.; Xu, X.; Yu, L.; Wang, Q.; Liu, H. Y. Effect of substituents on Mn-O bond in oxo-manganese(V) corrole complexes. Acta. Phys.-Chim. Sin. 2012, 28, 16581664.
(31) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Wallingford CT. Gaussian 03, Revision D.01 2004.
(32) Gong, L. Z.; Xu, Z. G.; Xu, X.; He, J.; Wang, Q.; Liu, H. Y. Axial coordination behavior of corrole MnIII and MnVO complexes with N-based ligands. Acta. Phys.-Chim. Sin. 2014, 30, 265272.
(33) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem. Rev. 1988, 88, 899926.
(34) Liu, J. J.; Wang, H. H.; Ying, X.; Wang, X. L.; Zhang, H.; Liu, H. Y. Stability of manganese-oxo corrole. Chem. J. Chin. Univ. 2011, 32, 218224.
(35) Zhu, C.; Cao, Z. X. Theoretical investigation on Mn-corrole catalyzed oxidation of cyclohexane to adipaldehyde. J. Mol. Sci. 2014, 30, 265272.
(36) Mandimutsira, B. S.; Ramdhanie, B.; Todd, R. C.; Wang, H.; Zareba, A. A.; Czernuszewicz, R. S.; Goldberg, D. P. A stable manganese(V)-oxo corrolazine complex. J. Am. Chem. Soc. 2002, 124, 1517015171.
(37) Wang, S. H.; Mandimutsira, B. S.; Todd, R.; Ramadhanie, B.; Fox, J. P.; Goldberg, D. P. Catalytic sulfoxidation and epoxidation with a Mn(III) triazacorrole: evidence for a “third oxidant” in high-valent porphyrinoid oxidations. J. Am. Chem. Soc. 2004, 126, 1819.
(38) Goldberg, D. P. Corrolazines: new frontiers in high-valent metalloporphyrinoid stability and reactivity. Acc. Chem. Res. 2007, 40, 626634.
(39) Prokop, K. A.; Neu, H. M.; de Visser, S. P.; Goldberg, D. P. A manganese(V)-oxo p-cation radical complex: influence of one-electron oxidation on oxygen-atom transfer. J. Am. Chem. Soc. 2011, 133, 1587415877.