CN111018895B - 一种四吡啶基卟啉锌-二十四核钌配合物及其制备和应用 - Google Patents
一种四吡啶基卟啉锌-二十四核钌配合物及其制备和应用 Download PDFInfo
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 34
- SBTXZBOBSRZUPE-UHFFFAOYSA-N 5,10,15,20-tetrapyridin-2-yl-21,23-dihydroporphyrin Chemical compound c1cc2nc1c(-c1ccccn1)c1ccc([nH]1)c(-c1ccccn1)c1ccc(n1)c(-c1ccccn1)c1ccc([nH]1)c2-c1ccccn1 SBTXZBOBSRZUPE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- -1 zinc-dimyristyl ruthenium Chemical compound 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 16
- AVAYXTKDRHARSR-UHFFFAOYSA-N [Zn].[Ru] Chemical compound [Zn].[Ru] AVAYXTKDRHARSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- GPCVIABQWNSPHL-UHFFFAOYSA-N N1=C(C=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=NC=CC=C5)N4)C4=NC=CC=C4)N3)C3=NC=CC=C3)=N2.[Ru].[Zn] Chemical compound N1=C(C=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=NC=CC=C5)N4)C4=NC=CC=C4)N3)C3=NC=CC=C3)=N2.[Ru].[Zn] GPCVIABQWNSPHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 229940125898 compound 5 Drugs 0.000 claims 1
- 150000004032 porphyrins Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006276 transfer reaction Methods 0.000 abstract description 2
- 150000003333 secondary alcohols Chemical class 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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Abstract
本发明公开了一种四吡啶基卟啉锌‑二十四核钌配合物的合成及其应用。在室温条件下，以配位不饱和的卟啉锌‑钌配合物为原料与含氮六齿配体在有机溶剂中发生配位反应，反应结束后经简单后处理，得到具有较高催化活性的四吡啶基卟啉锌‑二十四核钌配合物。此四吡啶基卟啉锌‑二十四核钌配合物可应用于氢转移反应中，是制备二级醇的简便绿色的方法。
Description
技术领域
本发明涉及一种四吡啶基卟啉锌-二十四核钌配合物及其制备方法，以配位不饱和的四吡啶基卟啉锌-钌配合物为原料，与含氮六齿配体在有机溶剂中发生配位反应，合成具有较高催化活性的四吡啶基卟啉锌-二十四核钌配合物。本发明具有操作简便、反应条件温和、合成效率高等优点。
技术背景
配位驱使的组装反应被广泛应用于合成不同类型的超分子化合物，如索烃、节状化合物等。这些超分子化合物在材料、光化学、电化学等方面存在潜在的应用前景。
近年来，利用卟啉作为前体合成各种类型的超分子化合物受到了广泛的关注，通过不同的组装与反应方式可以得到立体构型各异的卟啉超分子配合物，在多种催化领域有着较好的应用前景。2015年，Ema研究组(T.Ema, et al.Angew.Chem.Int.Ed.2015,54,134.)合成不同类型的卟啉锌及卟啉镁的超分子化合物，并成功应用于二氧化碳对环氧化合物的插入反应，高效的制备碳酸酯化合物，在材料及电化学方向有着潜在的应用价值。Anderson 研究组(H.L.Anderson,et al.Angew.Chem.Int.Ed.2016,55,8358.)以五齿配体为模板剂成功合成了卟啉锌超分子环状化合物，具有较好的光化学性能。 Kobayashi研究组(K.Kobayashiet,et al.J.Am.Chem.Soc.2016,138,12564.) 利用卟啉铑配合物为前体，与具有多配位点的分子进行配位组装，通过调变官能团的不同，合成了不同类型的超分子卟啉铑配合物，并进行了单晶、核磁等一系列表征，在主客体化学中有广泛的应用前景。
本发明主要是利用含氮六齿配体与配位不饱和的四吡啶基卟啉锌-钌作用，四吡啶基卟啉锌-钌配合物中锌金属中心具有一个空位，可与含氮六齿配体中配位性的原子进行配位，合成具有较高氢转移活性的四吡啶基卟啉锌-二十四核钌配合物，制备方法简单、产率高。此类四吡啶基卟啉锌-二十四核钌配合物性质稳定，对空气不敏感，易于保存。
发明内容
本发明的目的在于提供一种操作简便、反应条件温和、高收率的制备四吡啶基卟啉锌-二十四核钌配合物的方法。该四吡啶基卟啉锌-二十四核钌配合物性质稳定，对空气不敏感，易于保存。
为了实现上述目的，本发明的技术方案如下：
1.一种四吡啶基卟啉锌-二十四核钌配合物，其结构式1如下：
利用四吡啶基卟啉锌-钌配合物2与含氮六齿配体3在有机溶剂中进行反应合成四吡啶基卟啉锌-二十四核钌配合物1；
含氮六齿配体3的结构式如下：
X取代基为无或者乙炔基。
四吡啶基卟啉锌-二十号四核钌配合物1的合成路线如下述反应式所示：
四吡啶基卟啉锌-钌配合物2与含氮六齿配体3的反应溶剂为二氯甲烷、甲醇、乙醇和甲苯中的一种或者两种以上。
四吡啶基卟啉锌-钌配合物2与含氮六齿配体3的摩尔比范围为1:1-10:1，四吡啶基卟啉锌-钌配合物2与含氮六齿配体3的摩尔比优选为2:1。
四吡啶基卟啉锌-钌配合物2与含氮六齿配体3的反应温度为20-110℃，优选为78℃；反应时间为1-24h。
反应气氛为氮气，压力条件为一个大气压。
将反应体系减压浓缩后用二氯甲烷/正己烷(v/v＝1/3)重结晶即可得到四吡啶基卟啉锌-二十四核钌配合物1。
所述酮类化合物4其结构如下式所示：
结构式中的R1为碳原子数为1-4的烷基、芳基、萘基、吡啶基、呋喃基或噻吩基；
R2为碳原子数为1-10的烷基、苯基或萘基。氮气氛围下异丙醇中回流，在0.0125mol％Ru-0.05mol％Ru浓度下，即可将酮类化合物转化为相应的醇类化合物。
本发明具有以下优点：
1)四吡啶基卟啉锌-二十四核钌配合物合成路线简单，条件温和，可方便快捷的合成出目标产物。
2)四吡啶基卟啉锌-二十四核钌配合物性质稳定，对空气不敏感，易于保存。
3)四吡啶基卟啉锌-二十四核钌配合物可用于高效催化酮的氢转移反应。
具体实施方式
本发明以四吡啶基卟啉锌-钌配合物2为原料，与含氮六齿配体3按6:1 摩尔比在有机溶剂中发生配位反应，合成四吡啶基卟啉锌-二十四核钌配合物1。通过下述实施例有助于进一步理解本发明，但本发明的内容并不仅限于此。
实施例1
氮气条件下，配位不饱和的四吡啶基卟啉锌-钌配合物2(207mg,0.06 mmol)、含氮六齿配体(X为无)3a(10mg,0.01mmol)，在5mL的乙醇溶剂中78℃搅拌1h。减压下除去挥发组份，固体用CH2Cl2/正己烷(v:v＝1:3) 重结晶，得到红绿色固体为目标产物1a(206mg，收率95％)。
实施例2
反应步骤与操作同实施例1，与实施例1不同之处在于，体系反应时间为24h。停止反应后，经后处理得到红绿色固体为目标产物1a(206mg,收率95％)。说明延长反应时间对增加目标产物收率无益。
实施例3
反应步骤与操作同实施例1，与实施例1不同之处在于，反应溶剂为甲苯，反应温度为110℃。停止反应后，经后处理得到红绿色固体为目标产物1a(202mg,收率93％)。说明在非质子性溶剂中也能进行此反应。
实施例4
反应步骤与操作同实施例1，与实施例1不同之处在于，反应溶剂为二氯甲烷/甲醇(v/v,5/1)，反应温度为28℃。停止反应后，经后处理得到红绿色固体为目标产物1a(193mg,收率89％)。说明在混合溶剂中也能进行此反应。
实施例5
反应步骤与操作同实施例1，与实施例1不同之处在于，体系反应温度为50℃。停止反应后，经后处理得到红绿色固体为目标产物1a(174mg, 收率80％)。
实施例6
反应步骤与操作同实施例1，与实施例1不同之处在于，体系反应温度为20℃。停止反应后，经后处理得到红绿色固体为目标产物1a(156mg, 收率72％)。
实施例7
在氮气保护下，将四吡啶基卟啉锌-二十四核钌配合物1a(5.0μmol)溶于20.0mL异丙醇中配成催化剂溶液。在氮气保护下，将底物苯乙酮(2.0 mmol)、2mL催化剂溶液和17.6mL异丙醇的混合物在82℃搅拌5分钟。然后将0.4mL iPrOK的异丙醇溶液(0.05M)加入反应体系中。在指定的时间内，抽取0.1mL的反应液，并立即用0.5mL异丙醇稀释后做气相色谱分析。在所述条件下，苯乙酮几乎定量的还原为对应的醇产物，说明本发明的配合物可作为潜在的酮还原催化剂使用。
典型化合物表征数据
四吡啶基卟啉锌-二十四核钌配合物1a,红绿色固体，M.p.:>300℃dec. 1H NMR(DMSO-d6,400MHz,23℃)δ9.01(d,J＝3.8Hz,48H),8.84(s,48 H),8.43(d,J＝3.2Hz,12H),8.22(d,J＝3.6Hz,48H),8.07(d,J＝8.2Hz,24 H),7.62(t,J＝8.0Hz,36H),7.56(d,J＝7.7Hz,24H),7.44(d,J＝7.7Hz,36 H),7.31(d,J＝8.4Hz,24H),7.22(t,J＝8.0Hz,216H),7.06(t,J＝7.2Hz, 156H),7.02-6.92(m,48H),6.38(s,24H),2.69(s,72H),2.53(s,72H).13C{1H}NMR(100MHz,DMSO-d6,23℃)δ160.0,156.7,155.1,151.5,151.3, 150.3,148.6,148.0,146.8,146.0,144.5,135.8,133.3,133.2,132.9(d,J＝10 Hz),132.0,131.6,131.4,129.3,129.0,128.82,128.75,127.6(d,J＝8.8Hz), 120.6,120.4,119.7,118.7,118.1,117.2,116.3,112.5,112.2,108.0,14.5,14.2. 31P{1H}NMR(162Hz,DMSO-d6,23℃)δ33.5.IR(KBr pellets,cm-1):ν3439, 3053,2922,2556,2344,1958,1480,1459,1436,1413,1359,1328,1283,1204, 1159,1093,1072,1049,1028,995,923,893,874,848,793,748,698,619,578, 529,515,500,465,439.Anal.Calcd for C1152H888Cl24N174P24Ru24Zn6:C,64.11； H,4.15；N,11.29.Found:C,64.20；H,4.18；N,11.20。
Claims (9)
1.一种四吡啶基卟啉锌-二十四核钌配合物，其结构式1如下：
X处为此处无取代基。
2.一种权利要求1所述四吡啶基卟啉锌-二十四核钌配合物的合成方法，其特征在于：利用权利要求1中的配位不饱和的四吡啶基卟啉锌-钌配合物2与含氮六齿配体3在有机溶剂中进行反应合成四吡啶基卟啉锌-二十四核钌配合物1；
含氮六齿配体3的结构如下：
X处为无取代基；
四吡啶基卟啉锌-二十四核钌配合物1的合成路线如下述反应式所示：
3.按照权利要求2所述的合成方法，其特征在于：四吡啶基卟啉锌-钌配合物2与含氮六齿配体3的反应溶剂为二氯甲烷、甲醇、乙醇和甲苯中的一种或者两种以上。
4.按照权利要求2所述的合成方法，其特征在于：四吡啶基卟啉锌-钌配合物2与含氮六齿配体3的反应温度为20-110 oC,反应时间为1-24 h。
5.按照权利要求2所述的合成方法，其特征在于：反应气氛为氮气，压力条件为一个大气压。
6.按照权利要求2所述的合成方法，其特征在于：反应结束后，将反应体系减压浓缩后用二氯甲烷/正己烷(v/v = 1/3)重结晶即可得到四吡啶基卟啉锌-二十四核钌配合物1。
7.一种权利要求1所述四吡啶基卟啉锌-二十四核钌配合物作为酮类化合物还原催化剂的应用。
8.按照权利要求7所述的应用，其特征在于：所述酮类化合物4其结构如下式所示：
结构式中的R1为碳原子数为1-4的烷基、芳基、吡啶基、呋喃基或噻吩基；
R2为碳原子数为1-10的烷基、苯基或萘基。
9.按照权利要求7或8所述的应用，其特征在于：氮气氛围下异丙醇中回流，在0.0125mol% Ru-0.05 mol% Ru浓度下，即可将酮类化合物转化为相应的醇类化合物，所述醇类化合物5其结构如下式所示：
结构式中的R1为碳原子数为1-4的烷基、芳基、吡啶基、呋喃基或噻吩基；
R2为碳原子数为1-10的烷基、苯基或萘基。
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