Strandberg型苯基膦钼酸-联咪唑荷移盐的合成及催化性能
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摘要
苯基膦酸(C_6H_5PO_3H_2)作为磷源,在温和条件下与Na_2MoO_4·2H_2O、2,2′-联咪唑(H2biim)反应,并借助H_2biim质子化后形成的有机阳离子[H_3biim]~+和杂多阴离子[(PhP)_2Mo_5O_(15)]~(4-)(PhP=C_6H_5PO_3)之间的电中和作用,在弱酸性水溶液中缓慢晶化,形成了1例以PhP为中心的Strandberg型苯基膦钼酸-联咪唑荷移盐(H_3biim)_4[(PhP)_2Mo_5O_(15)]·H_2O(1).利用单晶和粉末X射线衍射(SCXRD和PXRD)分析、元素分析、红外(IR)光谱等手段对化合物1进行了表征,并通过热重-差热分析(TG-DTA)考察了其热稳定性.以酸催化合成环己酮乙二醇缩酮为反应模型,探讨了化合物1的酸催化性能,同时考察了反应时间、反应物料比和催化剂用量对反应的影响.结果表明:化合物1作为固体多金属氧酸盐(POM)型催化剂,其催化活性高,结构稳定,可循环使用.
Phenylphosphonic acid(C_6H_5PO_3H_2)was used as the P source to react with Na_2MoO_4·2H_2O,2,2′-diimidazole(H_2biim)under mild conditions,and by the aid of charge neutralization between organic cation[H_3biim]~+ formed by protonation of H2 biim and heteropolyoxoanion [(PhP)_2Mo_5O_(15)]~(4-)(PhP = C_6H_5PO_3),a Strandberg-type phenylphosphomolybdate-H_2biim charge-transfer salt,(H)3biim)4[(PhP)2 Mo5 O15]·H2 O(1)with a PhP center,was obtained through slow crystallization in weak acidic aqueous solution.Compound 1 was characterized by single-crystal and powder Xray diffraction(SCXRD and PXRD)analysis,elemental analysis,IR spectroscopy.The thermal stability of compound 1 was also investigated by thermogravimetry and differential thermal analysis(TGDTA).The acid-catalytic synthesis of cyclohexanone ethylene ketal was selected as a model reaction,and the acid catalytic performance of compound 1 was evaluated,together with the effects of reaction time,material ratio and catalyst dosage on the reaction also were studied.The results show that compound 1 as a solid polyoxometalatc(POM)catalyst,has high catalytic activity,stable structure,and the catalyst can be recycled.
Phenylphosphonic acid(C_6H_5PO_3H_2)was used as the P source to react with Na_2MoO_4·2H_2O,2,2′-diimidazole(H_2biim)under mild conditions,and by the aid of charge neutralization between organic cation[H_3biim]~+ formed by protonation of H2 biim and heteropolyoxoanion [(PhP)_2Mo_5O_(15)]~(4-)(PhP = C_6H_5PO_3),a Strandberg-type phenylphosphomolybdate-H_2biim charge-transfer salt,(H)3biim)4[(PhP)2 Mo5 O15]·H2 O(1)with a PhP center,was obtained through slow crystallization in weak acidic aqueous solution.Compound 1 was characterized by single-crystal and powder Xray diffraction(SCXRD and PXRD)analysis,elemental analysis,IR spectroscopy.The thermal stability of compound 1 was also investigated by thermogravimetry and differential thermal analysis(TGDTA).The acid-catalytic synthesis of cyclohexanone ethylene ketal was selected as a model reaction,and the acid catalytic performance of compound 1 was evaluated,together with the effects of reaction time,material ratio and catalyst dosage on the reaction also were studied.The results show that compound 1 as a solid polyoxometalatc(POM)catalyst,has high catalytic activity,stable structure,and the catalyst can be recycled.
引文
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[3]LI X M,CHEN Y G,SHI T,et al.Coordination of the carboxylate of the functionalized Strandberg anion in a three dimensional covalence framework[J].Inorg Chem Commun,2014,50:70-74.
[4]DEY C,KUNDU T,BANERJEE R.Reversible phase transformation in proton conducting Strandberg-type POM based metal organic material[J].Chem Commun,2012,48(2):266-268.
[5]LU T,FENG S L,ZHU Z M,et al.Four Strandberg-type polyoxometalates with organophosphine center decorated by transition metal-2,2′-bipy/H2O complexes[J].J Solid State Chem,2017,253:52-57.
[6]FENG S L,LU Y,ZHANG Y X,et al.Three new Strandberg-type phenylphosphomolybdate supports for immobilizing horseradish peroxidase and their catalytic oxidation performances[J].Dalton Trans,2018,47(39):14060-14069.
[7]QU X S,FENG H,MA C,et al.Synthesis,crystal structure and anti-tumor activity of a novel 3Dsupramolecular compound constructed from Strandberg-type polyoxometalate and benzimidazole[J].Inorg Chem Commun,2017,81:22-26.
[8]DU J,CAO M D,FENG S L,et al.Two new Preyssler-type polyoxometalate-based coordination polymers and their application in horseradish peroxidase immobilization[J].Chem A Eur J,2017,23(58):14614-14622.
[9]SANG X J,FENG S L,LU Y,et al.A new hexamolybdate-based copper-2,2′-biimidazole coordination polymer serving as an acid catalyst and support for enzyme immobilization[J].Acta Cryst,2018,C74:1362-1369.
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[11]刘昭宇,朱浩天,卢明达,等.有机阳离子修饰的Strandberg型钼磷酸盐的合成、催化性能[J].应用化学,2015,32(2):214-220.
[12]XIAO J C,TWAMLEY B,SHREEVE J M.An ionic liquid-coordinated palladium complex:a highly efficient and recyclable catalyst for the heck reaction[J].Org Lett,2004,6(21):3845-3847.
[13]SHELDRICK G M.Crystal structure refinement with SHELXL[J].Acta Cryst,2015,C71:3-8.
[14]BROWN I D,ALTERMATT D.Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database[J].Acta Cryst,1985,B41:244-247.
[15]WEI L H,WANG Z L,WANG J P.Synthesis and structure investigation of a transition metal ion bridging bis(diphosphopentamolybdates),[H2BIIM]3[HBIIM]4[Mn(H2O)4(P2Mo5O23)2]·7H2O[J].Chinese J Struct Chem,2010,29(5):784-788.
[16]DE B P,ALDOUS A,LIU H X,et al.Hydrothermal chemistry of oxomolybdenum-1,4-carboxy-phenylphosphonates in the presence of M(Ⅱ)-organonitrogen building blocks(M(Ⅱ)=Co,Ni,and Cu)[J].Cryst Growth Des,2010,10(5):2209-2218.
[17]TAO D J,LI Z M,CHENG Z,et al.Kinetics study of the ketalization reaction of cyclohexanone with glycol using Brnsted acidic ionic liquids as catalysts[J].Ind Eng Chem Res,2012,51(50):16263-16269.
[18]LIU J H,WEI X F,YU Y L,et al.Uniform core-shell titanium phosphate nanospheres with orderly open nanopores:a highly active Brnsted acid catalyst[J].Chem Commun,2010,46(10):1670-1672.