Synthesis, Structure of an Iron(Ⅲ) Complex Containing N-Donor Ligand and Its Catalytic Activity for Cyclohexane Oxidation

doi:10.3724/SP.J.1095.2014.30439

Chinese Journal of Applied Chemistry

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Synthesis, Structure of an Iron(Ⅲ) Complex Containing N-Donor Ligand and Its Catalytic Activity for Cyclohexane Oxidation

XU Liting, XING Na^*, WU Qiong, MA Xitong, XING Yongheng^*

(College of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian 116029,China)

Received:2013-09-03 Revised:2013-11-05 Published:2014-06-10 Online:2014-06-10

Abstract

Abstract: One novel iron complex, [Fe(H2L)2]·(CH3COO)2·(OH)·H2O(H2L=2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine) with N-donor ligand 2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine, was synthesized and characterized by elemental analysis, powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction. In addition, the catalytic activity of the complex to cyclohexane oxidation was examined. The effects of various reaction factors such as the amount of H2O2, HNO3 and water, reaction time, as well as the temperature on the formation and decomposition of cyclohexylhydroperoxide, and the yield of C6H10O and C6H11OH were evaluated. The mechanism of oxidation reaction was also discussed. It shows that H2O2 is the main oxidant for the oxidation of cyclohexane to C6H11OOH catalyzed by the titled Fe complex; HNO3 has no oxidizing effect on this process, but can accelerate the formation and decomposition rates of C6H11OOH. Water has an inhibition effect on the catalytic activity, thereby lowering the formation and decomposition rates of C6H11OOH. The formation rates of C6H11OOH and C6H10O(C6H11OH) are different at different reaction stages. Higher temperature can promote the decomposition of C6H11OOH, which benefits the formation of C6H10O and C6H11OH.

Key words: iron complex,di-(methy-1H-pyrazol-yl)pyridine, cyclohexane oxidation, cyclohexylhydroperoxide, reaction mechanism

CLC Number:

O643

XU Liting, XING Na*, WU Qiong, MA Xitong, XING Yongheng*. Synthesis, Structure of an Iron(Ⅲ) Complex Containing N-Donor Ligand and Its Catalytic Activity for Cyclohexane Oxidation[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30439.

References

[1] Ishii Y,Sakaguchi S,Iwahama T. Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions[J]. Adv Synth Catal,2001,343(5):393-427.

[2] Eissen M,Metzger J,Schmidt E,et al. 10 Years after Rio-Concepts on the Contribution of Chemistry to a Sustainable Development[J]. Angew Chem Int Ed,2002,41(3):414-436.

[3] Eissen M,Metzger J,Schmidt E,et al. 10 Jahre nach “Rio” Konzepte zum Beitrag der Chemie zu einer Nachhaltigen Entwicklung[J]. Angew Chem Int Ed,2002,114(3):402-425.

[4] Mahmudov K T,Kopylovich M N,Guedes da Silva M F C,et al. New Copper(Ⅱ) Dimer with 3-(2-Hydroxy-4-nitrophenylhydrazo)pentane-2,4-dione and Its Catalytic Activity in Cyclohexane and Benzyl Alcohol Oxidations[J]. J Mol Catal A:Chem,2010,318(1/2):44-50.

[5] Dolaz M,McKee V,Urus S,et al. Synthesis, Structural Characterization, Catalytic, Thermal and Electrochemical Investigations of Bidentate Schiff Base Ligand and Its Metal Complexes[J]. Spectrochim Acta Part A,2010,76(2):174-181.

[6] GUO Cancheng,ZHANG Xiaobing,HOU Lianbo,et al. Stndy on the Mechanism of Cyclohexanone Formation in Cyclohexane Hydroxylation Catalyzed by Metalloporphyrins[J]. Acta Chim Sin,1998,56(5):489-494(in Chinese).

郭灿城,张晓兵,侯连伯,等. 金属卟啉催化环已烷轻基化反应中环己酮的形成机理研究[J]. 化学学报,1998,56(5):489-494.

[7] Niasari M S,Salimi Z,Bazarganipour M,et al. Synthesis, Characterization and Catalytic Oxidation of Cyclohexane Using a Novel Host(zeolite-Y)/guest(binuclear transition metal complexes) Nanocomposite Materials[J]. Inorg Chim Acta,2009,362(10):3715-3724.

[8] ZHAO Ruihua,DONG Mei,QIN Zhangfeng,et al. Synthesis and Characterization of CoAPO-5 with Different Cobalt Contents and Their Catalytic Performance for Cyclohexane Oxidation[J]. Acta Phys Chim Sin,2008,24(12):2304-2308(in Chinese).

赵瑞花,董梅,秦张峰,等. 不同钴含量 CoAPO-5分子筛的合成、表征及其催化环己烷氧化性能[J]. 物理化学学报,2008,24(12):2304-2308.

[9] Aboelfetoh E F,Fechtelkord M,Pietschnig R. Structure and Catalytic Properties of MgO-supported Vanadium Oxide in the Selective Oxidation of Cyclohexane[J]. J Mol Catal A:Chem,2010,318(1/2):51-59.

[10] Zhou L P,Xu J,Miao H,et al. Catalytic Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone over Co3O4 Nanocrystals with Molecular Oxygen[J]. Appl Catal A:General,2005,292:223-228.

[11] Xing N,Shan H,Zhao H Y,et al. Application in the Cyclohexane Oxidation of a Scorpionate Oxovanadium(Ⅳ) Complex:Synthesis, Structure, and Properties of VO(C5H7O2)(BC9H7N6I3)[J]. J Coord Chem,2012,65(5):898-910.

[12] Ren D X,Xing N,Shan H,et al. Novel Vanadium(Ⅲ) Complexes with Rigid Phenylpolycarboxylate Ligands: Synthesis, Structures and Application in C—H bond Activation[J]. Dalton Trans,2013,42(15):5379-5389.

[13] WAN Lijuan,XING Na,WAN Liying,et al. Synthesis, Structure and Properties of the Cadmium Complex Using Bisphenyl-pyrazolyl-pyridine Derivative and Oxalate as Mixed Ligand[J]. Chinese J Appl Chem,2012,29(11):1266-1271(in Chinese).

万丽娟,邢娜,万丽英,等. Cd（Ⅱ）双苯吡唑基吡啶-草酸混配合物的合成、结构与性质[J]. 应用化学,2012,29(11):1266-1271.

[14] Wan L J,Zhang C S,Xing Y H,et al. Neutral Mononuclear, Dinuclear, Tetranuclear d7/d10 Metal Complexes Containing Bis-Pyrazole/Pyridine Ligands Supported by 2,6-Bis(3-pyrazolyl)Pyridine:Synthesis, Structure, Spectra, and Catalytic Activity[J]. Inorg Chem,2012,51(12):6517-6528.

[15] Xing N,Shan H,Tian X,et al. Two New Scorpionate Oxomolybdenum(Ⅵ) poly-(pyrazolyl)borate Complexes:Synthesis, Structure, and Catalytic Performance in the Oxidation of Cyclohexane[J]. Dalton Trans,2013,42(2):359-363.

[16] XING Na,SHAN Hui,SONG Ge,et al. Syntheses， Structures and Properties of Two Half-sandwich Cobalt Carboxylate Complexes with Tris(pyrazolyl) borate Ligand[J]. Chem J Chinese Univ,2013,34(5):1041-1046(in Chinese).

邢娜,单辉,宋鸽,等. 两个半夹心型聚吡唑硼酸盐羧酸钴配合物的合成、结构及催化活性[J]. 高等学校化学学报,2013,34(5):1041-1046.

[17] Silva A R,Mouro T,Rocha J. Oxidation of Cyclohexane by Transition-metal Complexes with Biomimetic Ligands[J]. Catal Today,2013,203:81-86.

[18] Akashi T,Nakazawa J,Hikichi S. Iron Complex Immobilized Catalyst Based on β-ketiminate Ligand:Alkene Oxygenation Activity Depending on the Morphology of Silica Support and the Structures of Base Additives[J]. J Mol Catal A:Chem,2013,371:42-47.

[19] Carvalho N M F,Horn Jr A,Antunes O A C. Cyclohexane Oxidation Catalyzed by Mononuclear Iron(Ⅲ) Complexes[J]. Appl Catal A:General,2006,305(2):140-145.

[20] Zheng A X,Wang H F,L C N,et al. Reactions of Cadmium(Ⅱ) Nitrate with 4-(Trimethylammonio)benzenethiolate in the Presence of N-Donor Ligands[J]. Dalton Trans,2012,41(2):558-566.

[21] Craig G A,Costa J S,Roubeau O,et al. Local Coordination Geometry and Spin State in Novel FeⅡ Complexes with 2,6-Bis(pyrazol-3-yl)pyridine-Type Ligands as Controlled by Packing Forces:Structural Correlations[J]. Chem Eur J,2012,18(37):11703-11715.

[22] Shiga T,Ito N,Hidaka A,et al. Series of Trinuclear NiⅡLnⅢNiⅡ Complexes Derived from 2,6-Di(acetoacetyl)pyridine:Synthesis, Structure, and Magnetism[J]. Inorg Chem,2007,46(9):3492-3501.

[23] Zhou Y B,Zhang X M,Chen W Z,et al. Synthesis, Structural Characterization, and Luminescence Properties of Multinuclear Silver Complexes of Pyrazole-functionalized NHC Ligands Containing Ag-Ag and Ag-π Interactions[J]. J Organomet Chem,2008,693(2):205-215.

[24] Silva T F S,M. Silva F G,Mishra G S,et al. Synthesis and Structural Characterization of Iron Complexes with 2,2,2-tris(1-Pyrazolyl)ethanol Ligands:Application in the Peroxidative Oxidation of Cyclohexane Under Mild Conditions[J]. J Organomet Chem,2011,696(6):1310-1318.

[25] Ruiter G,Costa J S,Lappalainen K,et al. The System Iron(Ⅱ)/mpzbpy Mediates the H2O2 Oxidation of Cyclohexane and Cyclooctene and the Aerobic Oxidative Cleavage of Ascorbic Acid to Oxalate[J]. Inorg Chem Commun,2008,11(7):787-790.

[26] Pokutsa A,Kubaj Y,Zaborovskyi A,et al. The Effect of Oxalic Acid and Glyoxal on the VO(acac)2-catalyzed Cyclohexane Oxidation with H2O2[J]. A Appl Catal A:General,2010,390(1/2):190-194.

[27] HE Dugui,JI Hongbing,LUO Sirui,et al. Reaction Mechanism of Liquid-Phase Oxidation of Cyclohexane Catalyzed by Bi-Modified Vanadium-Phosphorous Oxide Catalyst[J]. Chinese J Catal,2006,27(4):365-368(in Chinese).

何笃贵,纪红兵,罗思睿,等. 铋改性的钒磷氧化物液相催化氧化环己烷的反应机理[J]. 催化学报,2006,27(4):365-368.

[28] Gruenwald K R,Kirillov A M,Haukka M,et al. Mono-, di- and Polynuclear Copper(Ⅱ) Compounds Derived from N-Butyldiethanolamine:Structural Features, Magnetism and Catalytic Activity for the Mild Peroxidative Oxidation of Cyclohexane[J]. Dalton Trans,2009,10(12):2109-2120.

[29] LUO Yiming,XIAO Linxiang,CHEN Zhe,et al. Syntheses, Spectral Properties of Novel Pyridine-2,6-dicarboxylic Acid Derivatives and the Ir Tb(Ⅲ) Complexes[J]. Chem Res Appl,2008,20(3):299-303(in Chinese).

罗一鸣,肖林香,陈哲,等. 新型吡啶衍生物及其Tb（Ⅲ）配合物的合成与光谱性质研究[J]. 化学研究与应用,2008,20(3):299-303.

[30] Zhou Y,Chen W,Wang D. Mononuclear, Dinuclear, Hexanuclear, and One-dimensional Polymeric Silver Complexes Having Ligand-supported and Unsupported Argentophilic Interactions Stabilized by Pincer-like 2,6-Bis(5-pyrazolyl)pyridine Ligands[J]. Dalton Trans,2008,11(11):1444-1453.

[31] LUO Yiming,CHEN Zhe,TANG Ruiren,et al. Study on Synthesis of 2,6-Bisbenzoylactyl Pyridine[J]. Chem React Eng Technol,2006,22(6):549-553(in Chinese).

罗一鸣,陈哲,唐瑞仁,等. 2,6-二苯甲酰乙酰基吡啶合成工艺的研究[J]. 化学反应工程与工艺,2006,22(6):549-553.

[32] Sheldrick G M. SHELX-97, Program for Crystal Structure Analysis[M]. University of Gottingen:Gottingen,Germany,1997.

[33] Roberts T D,Tuna F,Malkin T L,et al. An Iron(Ⅱ) Complex Exhibiting Five Anhydrous Phases, Two of which Interconvert by Spin-crossover with Wide Hysteresis[J]. Chem Sci,2012,3(2):349-354.

[34] Fern ndez T L,Souza E T,Visentin L C,et al. A New Oxo-vanadium Complex Employing an Imidazole-rich Tripodal Ligand:A Bioinspired Bromide and Hydrocarbon Oxidation Catalyst[J]. J Inorg Biochem,2009,103(4):474-479.

[35] Trofimenko S. Boron-pyrazole Chemistry:IV. Carbon- and Boron-substituted Poly[(1-pyrazolyl) borates][J]. J Am Chem Soc,1967,89(24):6288-6294.

Synthesis, Structure of an Iron(Ⅲ) Complex Containing N-Donor Ligand and Its Catalytic Activity for Cyclohexane Oxidation

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