CN108148096A - 一种六核钌nnn配合物及其制备和应用 - Google Patents
一种六核钌nnn配合物及其制备和应用 Download PDFInfo
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000003446 ligand Substances 0.000 claims abstract description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- -1 ketone compounds Chemical class 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000000034 method Methods 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
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006276 transfer reaction Methods 0.000 abstract description 2
- 150000003333 secondary alcohols Chemical class 0.000 abstract 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 2
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GJSJZQZEDAUFBH-UHFFFAOYSA-N benzene;pentan-3-one Chemical compound CCC(=O)CC.C1=CC=CC=C1 GJSJZQZEDAUFBH-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- 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
- B01J31/24—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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Abstract
本发明公开了一种六核钌金属配合物的合成及其应用。在室温条件下，以配位不饱和的钌金属配合物为原料与含氮六齿配体反应，合成具有较高催化活性的六核钌金属配合物。此六核钌金属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
本发明涉及一种六核钌NNN配合物及其制备方法，以配位不饱和的单核钌金属配合物为原料，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六核钌NNN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
吡啶基氮杂环配体易与过渡金属配位，所形成的金属配合物较稳定，已成功应用于交叉偶联、催化氢化、Michael加成、环丙烷化和烯丙基取代等反应中。
近年来，多核金属配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多核金属配合物，在多种催化领域有着较好的应用前景。2008年，Anderson小组(Anderson,H.L.et al.Angew.Chem.Int.Ed.2008,47,4993.)利用六齿linker作为模板剂成功合成了纳米环状卟啉锌超分子化合物，相对于链状的卟啉锌超分子，纳米环状的超分子具有更好的π共轭效应。Stang研究组(Stang,P.J.etal.J.Am.Chem.Soc.2016,138,4580.)利用双铂配合物及双吡啶linker自组装，成功制备了金属环状超分子化合物，并研究其光物理性能，在生物技术及分子电子方面有着一定的应用前景。Li研究组(Li,X.P.et al.J.Am.Chem.Soc.2015,137,1556.)利用铂的金属前体与多齿linker自组装，通过改变两者之间的配比，就可得到2D或者3D结构的超分子化合物，在主客体化学及模板导向合成上有潜在的应用前景。
本发明主要是利用吡啶基氮杂环配体配位的单核钌金属配合物与含氮六齿配体作用，单核钌金属配合物中金属中心具有一个空位，可与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六核钌NNN配合物，制备方法简单、产率高。此类六核钌NNN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、高收率的制备六核钌NNN配合物的方法。该六核钌NNN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：
1.一种六核钌NNN配合物，其结构式1如下：
S取代基为苯基或者苯乙炔基。
利用配位不饱和的单核钌金属配合物2与含氮六齿配体3在有机溶剂中进行反应合成六核钌NNN配合物1；
含氮六齿配体3的结构式如下：
S取代基为苯基或者苯乙炔基。
六核钌NNN配合物1的合成路线如下述反应式所示：
单核钌金属配合物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。
单核钌金属配合物2与含氮六齿配体3的摩尔比范围为1:1-10:1，单核钌金属配合物2与含氮三齿配体3的摩尔比优选为6:1。
单核钌金属配合物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)重结晶即可得到六核钌NNN配合物1。
所述酮类化合物为芳香酮，脂肪酮。
氮气氛围下异丙醇中回流，在较低催化剂浓度下，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)六核钌NNN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)制备得到的六核钌NNN配合物性质稳定，对空气不敏感，易于保存。
3)六核钌NNN配合物可用于高效催化酮的氢转移反应。
具体实施方式
本发明以单核钌金属配合物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，合成六核钌NNN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。
单核钌金属配合物2按文献方法制备(Yu,Z.K.et al.Organometallics2008,27,2898.)；含氮六齿配体的3按文献方法制备(Anderson,H.L.et al.Angew.Chem.Int.Ed.2008,47,4993.)
实施例1
氮气条件下，配位不饱和的单核钌金属配合物2(41mg,0.06mmol)、三齿配体3a(10mg,0.01mmol)，在3mL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＝1:2)重结晶，得到红棕色固体为目标产物1a(48mg，收率94％)。目标产物通过核磁共振谱与元素分析测定得到确认。
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，经后处理得到红棕色固体为目标产物1a(45mg,收率88％)。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，经后处理得到红棕色固体为目标产物1a(42mg,收率82％)。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，经后处理得到红棕色固体为目标产物1a(46mg,收率90％)。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，经后处理得到红棕色固体为目标产物1a(40mg,收率78％)。
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，经后处理得到红棕色固体为目标产物1a(32mg,收率63％)。
实施例7
反应步骤与操作同实施例1，与实施例1不同之处在于，反应体系中加入的是三齿配体3b(11mg,0.01mmol)。停止反应后，经后处理得到红棕色固体为目标产物1b(50mg,收率96％)。目标产物通过核磁共振谱与元素分析测定得到确认。
实施例8
在氮气保护下，将三核钌NNN配合物1(2.5μmol)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(2.0mmol)、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
六核金属配合物1a，红棕色固体。Dark red solid.M.p.:>300℃,1H NMR(DMSO-d6,400MHz,23℃)δ8.42and 8.08(d each,12:12H,2″′-H and 3-H),7.55-7.64(m,6:6:12H,4-H,5-H and 3″′-H),7.43(t,12:12H,8″′-H and 9″′-H),7.31(d,6H,5″-H),7.16-7.24(m,54H,Ph in PPh3),7.04-7.11(m,36:6:6H Ph in PPh3,7″-H and 8″-H),6.98(t,6H,6″-H),6.37(s,6H,4′-H),2.69(s,18H,C3′-CH3),2.53(s,18H,C5′-CH3).13C{1H}NMR(DMSO-d6,100MHz,23℃)δ160.1,156.7,155.3,151.5,150.1,147.0,146.1,139.7,135.8,131.5,131.4,128.8(Cq each),132.9(d,o-C of PPh3),131.8(d,i-C PPh3),129.2(s,p-C ofPPh3),127.6(d,m-C of PPh3),144.5,128.7,127.5,124.9,120.5,120.4,119.5,118.7,117.1,116.1,112.4,107.9(CH),14.4(s,C3′-CH3),14.1(s,C5′-CH3).31P{1H}NMR(DMSO-d6,162MHz,23℃)δ33.5.Anal.Calcd for C282H222Cl6N36P6Ru6:C,66.15；H,4.37；N,9.85.Found:C,63.06；H,4.51；N,9.69.
六核金属配合物1b，橙黄色固体。Dark red solid.M.p.:>300℃,1H NMR(DMSO-d6,400MHz,23℃)δ8.57(d,12H,2″′-H),8.16and 7.70(d and m,6:12H,3-H,4-H and 5-H),7.38-7.51(m,24H,5″-H,8″-H and 3″′-H),7.19-7.24(m,54:6:12H,Ph in PPh3,6″-H and10″′-H),7.02-7.12(m,36:6:12H,Ph in PPh3,7″-H and 11″′-H),6.39(s,6H,4′-H),2.70(s,18H,C3′-CH3),2.54(s,18H,C5′-CH3).13C{1H}NMR(DMSO-d6,100MHz,23℃)δ157.0,153.7,151.6,151.4,145.0,144.9,140.6,139.4,130.4,130.0,125.7(Cq each),131.5(d,i-C of PPh3),149.9,136.1,132.8(d,o-C of PPh3),129.4,127.7(d,m-C of PPh3),125.3,121.5,118.8,117.7,116.8,112.6,121.1,117.3and 108.7(CH),93.3and87.0(C≡C,Cq each),14.4(C3′-CH3),14.1(C5′-CH3).31P{1H}NMR(DMSO-d6,162 MHz,23℃)δ33.0.Anal.Calcd for C294H222Cl6N36P6Ru6:C,67.08；H,4.25；N,9.58.Found:C,67.15；H,4.34；N,9.55.
Claims (10)
1.一种六核钌NNN配合物，其结构式1如下：
S取代基为苯基或者苯乙炔基。
2.一种权利要求1所述六核钌NNN配合物的制备方法，其特征在于：利用配位不饱和的单核钌金属配合物2与含氮六齿配体3在有机溶剂中进行反应合成六核钌NNN配合物1；
含氮六齿配体3的结构如下：
S取代基为苯基或者苯乙炔基；
六核钌NNN金属配合物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：单核金属配合物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：单核金属配合物2与含氮六齿配体3的摩尔比范围为1:1-10:1。
5.按照权利要求2所述的合成方法，其特征在于：单核金属配合物2与含氮六齿配体3的反应温度为20-110℃,反应时间为1-24h。
6.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。
7.按照权利要求2所述的合成方法，其特征在于：将反应体系减压浓缩后用二氯甲烷/正己烷(v/v＝1/3)重结晶即可得到六核钌NNN配合物1。
8.一种权利要求1所述六核钌NNN配合物作为酮类化合物还原催化剂的应用。
9.按照权利要求8所述的应用，其特征在于：所述酮类化合物为芳香酮，脂肪酮中的一种或二种以上。
10.按照权利要求8所述的应用，其特征在于：氮气氛围下异丙醇中回流，在催化剂存在下，即可将酮类化合物转化为相应的醇类化合物。
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| CN111018895A (zh) * | 2018-10-09 | 2020-04-17 | 中国科学院大连化学物理研究所 | 一种四吡啶基卟啉锌-二十四核钌配合物及其制备和应用 |
| CN111018895B (zh) * | 2018-10-09 | 2022-05-31 | 中国科学院大连化学物理研究所 | 一种四吡啶基卟啉锌-二十四核钌配合物及其制备和应用 |
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