【作者】 李杰；

【导师】 王敬平； 牛景杨；

【作者基本信息】 河南大学 ， 化学 无机化学， 2016， 硕士

【摘要】 本文采用常规水溶液法,从钨酸盐或多酸前驱体出发,通过不断地探索反应条件,成功合成出六例结构新颖的多钨、钒氧簇羰基金属衍生物。并通过红外、X-射线单晶衍射、元素分析、紫外-可见、X-射线粉末衍射、电喷雾质谱等手段对化合物进行表征。同时,对部分化合物的电化学行为以及催化性质进行了研究。1.首次合成出基于单缺位Linqvist型[W5018]6-阴离子的羰基金属衍生物：KH[(CH3)4N]3[{Re(CO)3}4(μ2-OH)(μ3-O)(W5O18)]·6H20 (1)。化合物阴离子由[W5018]6-同时担载四个羰基铼基团而成,是目前担载羰基金属基团数目最多的同多钨酸盐羰基金属衍生物。2.成功合成了一例基于[W8030]12-阴离子的担载型羰基金属衍生物：Na4H2[{Re(CO)3}2{Re(CO)3(H2O)}2(H2W8O30)]·19H2O(2),该化合物阴离子中存在一个晶体学反演中心。3.成功合成了一例新颖的类夹心型杂多钨酸盐羰基金属衍生物：[(CH3)4N]H11[{Mn(CO)3}2(H2O)2(W2O5)(HBW11O39)2]·45H2O(3),化合物阴离子由两个相同的{HBW11O39}单元分别担载一个羰基锰基团后通过两个{W06}八面体连接形成。4.成功合成了一例新颖的嵌入型杂多钨酸盐羰基金属衍生物：K2H2[(CH3)4N]3[{Re(CO)3}2(μ-OH)(HBW11O39)]·12H2O(4),该化合物阴离子中,两个相连接的羰基金属基团,通过四个Re-O-W键嵌入到多酸阴离子的缺位处。5. 首次合成了两例离子型钒氧簇羰基金属衍生物：H2[Mn(CO)3(C3H3N2)3]2[V2O7]·4H2O (5)和[Mn(CO)3(C3H3N2)3]6[V10O28]·3H2O (6)化合物5和6均在催化二氧化碳环加成反应中表现出较好的催化活性。化合物的组成和晶体学数据如下：1.KH[(CH3)4N]3[{Re(CO)3}4(μ2-OH)(μ3-O)(W5O18)]·6H2O(1):晶体属于单斜晶系,P2(1)/c空间群,晶胞参数：a=13.8745(8)A,b=19.1737(11)A,c=22.0448(13)A,β= 105.3700(10)°,Z=4,R1=0.0328,wR2=0.0715[I≥2σ(I)].2.Na4H2[{Re(CO)3}2{Re(CO)3(H2O)}2(H2W8O30)·19H2O(2):晶体属于单斜晶系,P2(1)/n空间群,晶胞参数：a=11.9571(14)A,b=16.354(2)A,c=17.740(2)A,β= 94.271(2)°,Z=2,R1=0.0662,wR2=0.1818[I≥2σ(I)].3.[(CH3)4N]H11[{Mn(CO)3}2(H2O)2(W2O5)(HBW11O39)2]·45H2O(3):晶体属于正交晶系,Cmce空间群,晶胞参数：a=45.791(3)A,b=24.8969(16)A,c=31.891(2)A,Z=8, R1=0.0846,wR2=0.1813[I≥2σ(I)].4.K2H2[(CH3)4N]3[{Re(CO)3}2(μ-OH)(HBW11O39)]·12H2O(4):晶体属于单斜晶系,P2(1)/c空间群,晶胞参数：a=15.4080(14)A,b=22.060(2)A,c=22.197(2)A,β= 104.395(2)°,Z=4,R1=0.0480,wR2=0.1158[I≥2σ(I)].5.H2[Mn(CO)3(C3H3N2)3]2[V2O7]·4H2O(5):晶体属于单斜晶系,P2(1)/c空间群,晶胞参数：a=16.1422(17)A,b=28.785(3)A,c=8.4175(9)A,β=99.216(2)°,Z=4,R1= 0.0400,wR2=0.1041[I≥2σ(I)].6.[Mn(CO)3(C3H3N2)3]6[V10O28]·3H2O(6):晶体属于单斜晶系,P2(1)/c空间群,晶胞参数：a=30.060(7)A,b=12.989(3)A,c=30.109(7)A,β=101.526(5)°,Z=4,R1= 0.0525,wR2=0.1214 [I≥2σ(I)].更多还原

【Abstract】 By the method of conventional aqueous solution, from simple tungstic acid salt and polyoxometalate precursor through constantly exploring reaction conditions, six novel type and structure of the polyoxotungstates and isopolyoxovanadates-based metal carbonyl derivatives were successfully synthesized, which were characterized by IR, X-ray single crystal diffraction, elemental analysis, UV-Vis and X-ray powder diffraction. At the same time, some of the compounds were discussed the electrochemical behavior and catalytic properties.1. A novel monolacunary Linqvist type isotungstate-supported metal carbonyl derivative KH[（CH₃）₄N]₃[{Re（CO）₃}₄（μ₂-OH）（μ₃-O）(W₅O₁₈)]·6H₂O（1） has been synthesized for the first time, whose anionic [W₅O₁₈]^6- carrys four rhenium carbonyl groups. And the compound carrys the highest number of metal carbonyl groups in isotungstate-supported metal carbonyl derivative.2. A novel [W₈O₃₀]^12- based metal carbonyl derivative Na₄H₂[{Re（CO）₃}₂{Re（CO）₃（H₂O）}₂(H₂W₈O₃₀)]·19H₂O（2） has been synthesized, whose polyoxoanion exists a crystallography inversion center.3. A novel heterpolytungstate-supported metal carbonyl derivative [（CH₃）₄N]H₁₁[{Mn（CO）₃}₂（H₂O）₂（W₂O₅）(HBW₁₁O₃₉)₂]·45H₂O（3） has been synthesized. The polyoxoanion of the compound consisted of two {HBW₁₁O₃₉} connect a manganese carbonyl unit respectively through two {WO₆} units together.4. A novel kind of sandwich type heterpolytungstate-supported metal carbonyl derivative K₂H₂[（CH₃）₄N]₃[{Re（CO）₃}₂（μ-OH）(HBW₁₁O₃₉)]·12H₂O（4） has been synthesized. There are two rhenium carbonyl units in the anonic, which embedded into the vacant polyoxometalate by four Re-O-W bonds.5. Two novel vanadium oxygen clusters-based metal carbonyl derivatives: H₂[Mn（CO）₃（C₃H₃N₂）₃]₂[V₂O₇]·4H₂O（5） and [Mn（CO）₃（C₃H₃N₂）₃]₆[V₁₀O₂₈]·3H₂O（6） has been synthesized for the first time, both of them represent the good activity in catalytic CO₂ cycloaddition reaction.更多还原