邻菲啰啉二氧钼(Ⅵ)配合物合成及催化环氧化性能
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摘要
通过邻菲啰啉分别与乙酰丙酮钼和二氯氧钼反应,合成了两个邻菲啰啉二氧钼(Ⅵ)配合物,并通过红外光谱、氢核磁共振谱、元素分析和紫外可见光谱方法表征。以1,2-二氯乙烷为溶剂、叔丁基过氧化氢为氧化剂探讨了邻菲啰啉钼(Ⅵ)配合物催化环氧化性能,结果表明,邻菲啰啉钼(Ⅵ)配合物具有很好的催化环氧化性能。在优化实验条件下,环氧化产物的选择性大于95%,底物的转化率均大于82%。烯键的催化环氧化活性顺序为:1-甲基环己烯>1-己烯>环己烯>α-甲基苯乙烯>4-氯苯乙烯>苯乙烯>α,β-不饱和羧酸酯。催化剂重复利用5次,催化活性基本保持稳定。
1,10-Phenanthroline dioxomolybdenum( VI) complexes were synthesized by the reaction of 1,10-Phenanthroline with MoO_2( acac)_2and Mo O_2Cl_2( THF)_2,which were characterized by IR,~1HNMR,element analysis and UV-Vis spectrum,respectively.The complexes were evaluated as catalyst for the epoxidation using tert-butylhydroperoxide( TBHP) as oxidant and 1,2-dichloroethane as solvent. The results showed that the complexes had an excellent catalytic epoxidation. Under the optimal experiment conditions,the selectivity of epoxides was more than 95%; the substrate conversion was higher than 82%.The order of catalytic epoxidation activity was as follows: 1-methylcyclohexene>1-hexene>cyclohexene>α-methylstyrene>4-chlorostyrene>styrene>α,β-unsaturated carboxylic ester.The catalytic activity was maintained after 5 reuses.
1,10-Phenanthroline dioxomolybdenum( VI) complexes were synthesized by the reaction of 1,10-Phenanthroline with MoO_2( acac)_2and Mo O_2Cl_2( THF)_2,which were characterized by IR,~1HNMR,element analysis and UV-Vis spectrum,respectively.The complexes were evaluated as catalyst for the epoxidation using tert-butylhydroperoxide( TBHP) as oxidant and 1,2-dichloroethane as solvent. The results showed that the complexes had an excellent catalytic epoxidation. Under the optimal experiment conditions,the selectivity of epoxides was more than 95%; the substrate conversion was higher than 82%.The order of catalytic epoxidation activity was as follows: 1-methylcyclohexene>1-hexene>cyclohexene>α-methylstyrene>4-chlorostyrene>styrene>α,β-unsaturated carboxylic ester.The catalytic activity was maintained after 5 reuses.
引文
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[2]Schachner J A,Traar P,Sala C,et al.Dioxomolybdenum(VI)complexes with pyrazole based aryloxide ligands:synthesis,characterization and application in epoxidation of olefins[J].Inorg Chem,2012,51(14):7 642-7 649.
[3]DupéA,Hossain M K,Schachner J A,et al.Dioxomolybdenum(VI)and-tungsten(VI)complexes with multidentate aminobisphenol ligands as catalysts for olefin epoxidation[J].Eur J Inorg Chem,2015,(21):3 572-3 579.
[4]Yang Y,Chattopadhyay S,Shibata T,et al.Covalent heterogenization of discrete bis(8-quinolinolato)dioxomolybdenum(VI)and dioxotungsten(VI)complexes by a metaltemplate/metal-exchange method:cyclooctene epoxidation catalysts with enhanced performances[J].J Mol Catal A:Chem,2014,392:134-142.
[5]孙斌,李贤均.N,N’-双(2’-羟基苯乙酮)缩二胺合锰(Ⅲ)的合成和催化烯烃环氧化研究[J].化学研究与应用,2012,24(6):926-931.
[6]Mayilmurugan R,Traar P,Schachner J A,et al.Dioxidomolybdenum(VI)complexes containing ligands with the bipyrrolidine backbone as efficient catalysts for olefin epoxidation[J].Eur J Inorg Chem,2 013,(21):3 664-3 670.
[7]Moradi-Shoeili Z,Boghaei D M,Amini M,et al.New molybdenum(VI)complex with O N S-donor thiosemicarbazone ligand:preparation,structural characterization,and catalytic applications in olefin epoxidation[J].Inorg Chem Commun,2013,27:26-30.
[8]Wong Y,Ng D K P,Lee H K.New chloro,μ-oxo,and alkyl derivatives of dioxomolybdenum(vi)and-tungsten(VI)complexes chelated with N2O tridentate ligands:synthesis and catalytic activities toward olefin epoxidation[J].Inorg Chem,2002,41(20):5 276-5 285.
[9]邓圣军,陈杰,钱浩,等.不对称铜配合物的合成,结构及其催化苯乙烯环氧化性能[J].化学研究和应用,2015,27(10):1 549-1 553.
[10]杨国玉,朱海林,周文峰,等.Co Pc/Al2O3催化分子氧环氧化环己烯的研究[J].化学研究和应用,2007,19(2):179-182.
[11]Coelho A C,Nolasco M,Balula S S,et al.Chemistry and catalytic activity of molybdenum(VI)-pyrazolylpyridine complexes in olefin epoxidation.crystal structures of monomeric dioxo,dioxo-μ-oxo,and oxodiperoxo derivatives[J].Inorg Chem,2011,50(2):525-538.
[12]Traar P,Schachner J A,Stanje B,et al.Dioxomolybdenum(VI)complexes with naphtholate-oxazoline ligands in catalytic epoxidation of olefins[J].J Mol Catal A:Chem,2014,385:54-60.
[13]Li Y D,Fu X K,Gong B W,et al.Synthesis of novel immobilized tridentate Schiff base dioxomolybdenum(VI)complexes as efficient and reusable catalysts for epoxidation of unfunctionalized olefins[J].J Mol Catal A:Chem,2010,322(1-2):55-62.
[14]Wang W L,Daran J C,Poli R,et al.OH-Substituted tridentate ONO Schiff base ligands and related molybdenum(VI)complexes for solvent-free(ep)oxidation catalysis with TBHP as oxidant[J].J Mol Catal A:Chem,2016,416:117-126.
[15]Bagherzadeh M,Zare M,Amini M,et al.Epoxidation of olefins catalyzed by a molybdenum-Schiff base complex anchored in the pores of SBA-15[J].J Mol Catal A:Chem,2014,395:470-480.
[16]Sj9gren M P T,Frisell H,kermark B,et al.Molybdenum-catalyzed allylic substitution.influence of 1,10-phenanthroline ligands on reactivity and selectivity[J].Organometallics,1997,16(5):942-950.
[17]Shirakawa E,Itoh K,Higashino T,et al.Tert-butoxide-mediated arylation of benzene with aryl halides in the presence of a catalytic 1,10-phenanthroline derivative[J].J Am Chem Soc,2010,132(44):15 537-15 539.
[18]Altman R A,Buchwald S L.4,7-Dimethoxy-1,10-phenanthroline:an excellent ligand for the Cu-catalyzed N-arylation of imidazoles[J].Org Lett,2006,8(13):2 779-2782.
[19]Zhang Y S,Hsung R P,Tracey M R,et al.Copper sulfatepentahydrate-1,10-phenanthroline catalyzed amidations of alkynyl bromides.synthesis of heteroaromatic amine substituted ynamides[J].Org Lett,2004,6(7):1 151-1154.
[20]Ebitani K,Fujie Y,Kaneda K.Immobilization of a ligandpreserved jgiant palladium cluster on a metal oxide surface and its nobel heterogeneous catalysis for oxidation of allylic alcohols in the presence of molecular oxygen[J].Langmuir,1999,15(10):3 557-3 562.
[21]Milko P,RoithováJ.Redox processes in the iron(III)/9,10-phenanthraquinone system[J].Inorg Chem,2009,48(24):11 734-11 742.
[22]柴凤兰,王向宇,张晓蓉,等.双二茂铁基醛亚胺钼(VI)配合物的合成及催化性能[J].分子催化,2009,23(5):422-428.
[23]Chai F L,Su H L,Wang X Y,et al.Synthesis and catalytic performance for olefin epoxidation of a novel dioxomolybdenum(VI)ferrocenyliminoalcoholate complex[J].Inorg Chim Acta,2009,362:3 840-3 844.
[24]Chai F L,Wang X Y,Tao J C.Preparation and catalytic activity of a new dioxomolybdenum(vi)complex for olefin epoxidation[J].React Kinet Catal Lett,2009,96(1):139-146.
[25]Arnaiz F J,Aguado R,Sanz-Aparicio J,et al.Addition compounds of dichlorodioxo-molybdenum(VI)from hydrochloric acid solutions of molybdenum trioxide.crystal structure of dichlorodioxodiaquamolybdenum(VI)bis(2,5,8-trioxanonane)[J].Polyhedron,1994,13(19):2 745-2 749.
[26]黄枢,谢如刚,田宝芝,等.有机合成试剂制备手册,第二版[M].北京:科学出版社,2005;43-44.
[27]Petrovski Z,Pillinger M,Valente A A,et al.Preparation and catalytic studies of bis(halogeno)dioxomolybdenum(VI)-diimine complexes[J].J Mol Catal A:Chem,2005,227(1-2):67-73.
[28]Bruno S M,Fernandes J A,Martins L S,et al.Dioxomolybdenum(VI)modified mesoporous materials for the catalytic epoxidation of olefins[J].Catal Today,2006,114(2~3):263-271.
[29]Petrovski Z,Braga S S,Santos A M,et al.Synthesis and characterization of the inclusion compound of a ferrocenyldiimine dioxomolybdenum complex with heptakis-2,3,6-tri-O-methyl-β-cyclodextrin[J].Inorg Chim Acta,2005,358(4):981-988.
[30]何其庄,王则民.稀土脯氨酸邻菲啰啉固体配合物合成和表征[J].无机化学学报,1999,15(6):721-726.