CN104447811A - 具有催化对甲基苯硼酸的蒽环双三唑-高氯酸铜配合物及其制备方法 - Google Patents
具有催化对甲基苯硼酸的蒽环双三唑-高氯酸铜配合物及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000000694 effects Effects 0.000 title abstract description 4
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 title abstract 4
- 229940045799 anthracyclines and related substance Drugs 0.000 title abstract 4
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 title abstract 4
- 238000007171 acid catalysis Methods 0.000 title abstract 2
- 239000010949 copper Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 7
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- 229910020366 ClO 4 Inorganic materials 0.000 claims description 26
- 150000004699 copper complex Chemical class 0.000 claims description 14
- 150000001454 anthracenes Chemical class 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 150000003852 triazoles Chemical class 0.000 claims description 10
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 abstract 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 2
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- -1 triazole copper complex Chemical class 0.000 description 2
- QHWTVIYSEHVEKU-UHFFFAOYSA-N Sc(c1c2cccc1)c(cccc1)c1c2S Chemical compound Sc(c1c2cccc1)c(cccc1)c1c2S QHWTVIYSEHVEKU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
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- 239000002798 polar solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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Abstract
本发明涉及具有催化对甲基苯硼酸的蒽环双三唑-高氯酸铜配合物及其制备方法,公开了一种{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH}( 1 )(tatrz=1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)的制备方法及作为催化对甲基苯硼酸偶联反应具有潜在的应用价值。它是采用“常温挥发法”,即Cu(ClO4)2和tatrz常温搅拌挥发条件下来制备该配合物。本发明进一步公开了{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH}( 1 )(tatrz=1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)可作为对甲基苯硼酸的偶联反应催化剂方面的应用。
Description
本发明得到国家自然科学基金面上项目(21471113),天津市教委项目资助(20140506),天津师范大学中青年教师学术创新推进计划项目和天津市高等学校创新团队培养计划资助(TD12-5038)。
技术领域
本发明属于无机合成技术领域,涉及铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)的制备方法及作为对甲基苯硼酸偶联反应的催化剂方面的应用。
背景技术
以过渡金属络合物催化进行高选择性合成的研究一直是一个活跃的领域。用普通合成手段难于实现的反应,有事使用过渡金属络合物能够在温和条件下一步完成。因此,采用金属络合物做催化剂来开发高选择性、高转化率的有机合成反应,是十分令人感兴趣的课题。有机合成中一般常用的过渡金属有镍、钯、铜、钌、铑、锰等,而其中钯络合物显示出多样性催化功能。钯催化偶联反应种类很多,这些反应在合成天然产物、聚合物、功能材料、液晶、药物分子及生物活性化合物中均有广泛的用途。但钯催化剂相对昂贵,如果能用廉价的铜配合物取代昂贵的钯催化剂,实现反应的进程,不仅可以节约成本,而且有望工业化生产。
1,2,4-三唑及其衍生物兼有吡唑和咪唑的配位特点,是配位能力较强的桥连配体,目前已合成并表征了大量的单核、多核和多维化合物。这些配体能够以1,2位上的氮原子与金属离子配位形成N1,N2-桥连模式,对于4位未取代的1,2,4-三唑衍生物能通过2,4位上的氮原子形成N2,N4-桥连模式,这种N2,N4-桥连模式同金属酶中咪唑的N1,N3-桥连模式类似。对于三唑类化合物的特殊用途还表现在分子器件化的设计上,合成具有不同维数的金属配合物乃是完成器件化至关重要的一步。
本发明即是选用Cu(ClO4)2和1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(tatrz)在常温条件下来制备铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1)。催化实验证明,该配合物可作为对甲基苯硼酸偶联反应的催化剂得以应用。
发明内容
本发明的另一个目的在于提供一种蒽环双三唑铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)单晶及其制备方法。
为此本发明人提供了如下的技术方案:
蒽环双三唑铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)的结构基元如图1所示。
本发明进一步公开了蒽环双三唑铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)的单晶,其特征在于该单晶结构采用APEX
II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线(λ = 0.71073 Å)为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出单晶数据:
表1. 配合物1的晶体学数据
本发明所述蒽环双三唑铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)单晶的制备方法,其特征在它是采用“常温挥发法”,即Cu(ClO4)2和tatrz常温搅拌挥发条件下来得到适合X-射线单晶衍射的黄色棒状晶体。其中CH3CN和H2O的体积比为4:6,Cu(ClO4)2和tatrz的摩尔比为1:1;
本发明更加详细的制备方法如下:
一种蒽环双三唑铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)单晶的制备方法,其特征在它采用“常温挥发法”,即Cu(ClO4)2和tatrz常温搅拌挥发条件下来得到适合X-射线单晶衍射的黄色棒状晶体。其中CH3CN和H2O的体积比为4:6,Cu(ClO4)2和tatrz的摩尔比为1:1;
本发明所述的溶剂为混合溶剂,CH3CN和H2O。
其中Cu(ClO4)2和tatrz的摩尔比为1:1。
本发明进一步公开了一种蒽环双三唑铜配合物具有催化对甲基苯硼酸偶联反应的作用。
本发明公开的一种蒽环双三唑铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)单晶所具有的优点和特点在于:
(1) 反应操作简便易行。
(2) 反应收率高,所得产品的纯度高。
(3) 本发明所制备的{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1) (tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)生产成本低,方法简便,适合大规模生产。
附图说明
图1:配合物1的晶体结构基元图;
图2:配合物1的三维结构图。
图3:4,4'-二甲基联苯的核磁图。
具体实施方式
下面结合实施例对本发明做进一步的说明,实施例仅为解释性的,决不意味着它以任何方式限制本发明的范围。所有的原料例如:蒽环等都是从国内外的化学试剂公司进行购买,没有经过继续提纯而是直接使用的。其中Cu(ClO4)2,CH3OH均由市售。
实施例1
1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(tatrz)配体的制备
在DMF极性溶剂中,将9,10-二溴蒽,三唑,碳酸钾和氧化铜在加热条件下制备该有机化合物;其中9,10-二溴蒽:三唑:碳酸钾:氧化铜的摩尔比为2:10:30:1;
反应温度1500℃,反应时间18小时。
实施例2
Cu(ClO4)2和1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(tatrz)的摩尔比为1:1;
tatrz (0.0312 g, 0.1 mmol)和Cu(ClO4)2 (0.0370 g, 0.1 mmol)在H2O (6 mL)和CH3OH
(4 mL)的混合溶剂中常温搅拌半小时后过滤,滤液常温挥发X-射线单晶衍射分析的黄色棒状晶体。产率:35% (基于tatrz计算)。元素分析(C40H44Cl2CuN12O14)
理论值(%):C,45.70;H,4.22;N,15.99。实测值:C,45.75;H,4.12;N,15.89。
实施例3
晶体结构测定采用APEX II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线(λ = 0.71073 Å)为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出晶体结构,并经洛仑兹和极化效应修正。所有的H原子由差值傅立叶合成并经理想位置计算确定。详细的晶体测定数据见表1。结构基元见图1,配合物的三维结构见图2。
表1. 配合物1的晶体学数据
实施例4
Cu(ClO4)2和1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(tatrz)的摩尔比为1:1;
我们还尝试过其他比例,比如Cu(ClO4)2和1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(tatrz)的摩尔比为2:1,则无论水热反应时间的长短,都得不到晶态化合物。因此Cu(ClO4)2和1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(tatrz)的摩尔比为1:1是最佳反应配比。
实施例5
以过渡金属络合物催化进行高选择性合成的研究一直是一个活跃的领域。用普通合成手段难于实现的反应,有事使用过渡金属络合物能够在温和条件下一步完成。因此,采用金属络合物做催化剂来开发高选择性、高转化率的有机合成反应,是十分令人感兴趣的课题。有机合成中一般常用的过渡金属有镍、钯、铜、钌、铑、锰等,而其中钯络合物显示出多样性催化功能。钯催化偶联反应种类很多,这些反应在合成天然产物、聚合物、功能材料、液晶、药物分子及生物活性化合物中均有广泛的用途。但钯催化剂相对昂贵,如果能用廉价的铜配合物取代昂贵的钯催化剂,实现反应的进程,不仅可以节约成本,而且有望工业化生产。
1,2,4-三唑及其衍生物兼有吡唑和咪唑的配位特点,是配位能力较强的桥连配体,目前已合成并表征了大量的单核、多核和多维化合物。这些配体能够以1,2位上的氮原子与金属离子配位形成N1,N2-桥连模式,对于4位未取代的1,2,4-三唑衍生物能通过2,4位上的氮原子形成N2,N4-桥连模式,这种N2,N4-桥连模式同金属酶中咪唑的N1,N3-桥连模式类似。对于三唑类化合物的特殊用途还表现在分子器件化的设计上,合成具有不同维数的金属配合物乃是完成器件化至关重要的一步。
本发明即是选用Cu(ClO4)2和1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(tatrz)在常温挥发条件下来制备铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1)。催化实验证明,该配合物可作为对甲基苯硼酸偶联反应的催化剂得以应用
在25 mL烧杯中称取1.1 g对甲基苯硼酸,0.2 g Cs2CO3,3 mL DMF和0.1 g催化剂(配合物1),室温下搅拌1小时,TLC监测(PE:EA = 1:1)反应完全,10 mL
CH2Cl2萃取产品后再用20 mL蒸馏水洗涤,有机相用污水MgSO4干燥,过滤,脱溶,得到的粗产品以石油醚洗脱过柱,得到4,4'-二甲基联苯。
Claims (4)
1.蒽环双三唑铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1)
(tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)的结构基元如图1所示。
2.权利要求1所述铜配合物的单晶,其特征在于该单晶结构采用APEX II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线(λ = 0.71073 Å)为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出单晶数据:
表1. 配合物1的晶体学数据
。
3.权利要求1所述铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1)
(tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)的制备方法,其特征在于它是采用“常温挥发法”,即Cu(ClO4)2和tatrz常温搅拌挥发条件下来制备该配合物;
所述的溶剂为混合溶剂为CH3OH和H2O;其中Cu(ClO4)2和1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑(L)的摩尔比为1:1。
4.权利要求1所述铜配合物{[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1)
(tatrz = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑)可作为对甲基苯硼酸的偶联反应催化剂方面的应用。
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JU-YAN LIU ET AL.: "Anion-Exchange and Anthracene-Encapsulation within Copper(II) and Manganese(II)-Triazole Metal-Organic Confined Space in a Single Crystal-to-Single Crystal Transformation Fashion", 《INORG. CHEM.》, vol. 53, no. 12, 27 May 2014 (2014-05-27), pages 5972 - 5985 * |
KASI PITCHUMANI ET AL.: "Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks", 《GREEN CHEMISTRY》, vol. 16, 24 February 2014 (2014-02-24), pages 2865 - 2875 * |
N KIRAI ET AL.: "Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air", 《EUR. J. ORG. CHEM.》, vol. 12, 31 December 2009 (2009-12-31), pages 1864 - 1867 * |
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