CN116332963A - 一种铜(i)配位化合物及其制备方法和应用 - Google Patents
一种铜(i)配位化合物及其制备方法和应用 Download PDFInfo
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- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000003446 ligand Substances 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 27
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 8
- WXGNSHNHXJXQNQ-UHFFFAOYSA-N 1h-pyrazol-5-ylphosphane Chemical compound PC=1C=CNN=1 WXGNSHNHXJXQNQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QYMFAVUZGLINNM-UHFFFAOYSA-N (2-fluorophenyl)-diphenylphosphane Chemical compound FC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QYMFAVUZGLINNM-UHFFFAOYSA-N 0.000 claims description 17
- XAKCEFMFWWQCCQ-UHFFFAOYSA-N phosphane 1H-pyrazole Chemical compound N1N=CC=C1.P XAKCEFMFWWQCCQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 12
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
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- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 claims 1
- MHFRLNRQWIWNRQ-UHFFFAOYSA-N oxido-oxo-(1H-pyrazol-5-yl)phosphanium Chemical compound O=P(=O)C=1C=CNN=1 MHFRLNRQWIWNRQ-UHFFFAOYSA-N 0.000 claims 1
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
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- 239000000975 dye Substances 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
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- QKLXBIHSGMPUQS-FGZHOGPDSA-M (3r,5r)-7-[4-(4-fluorophenyl)-2,5-dimethyl-1-phenylpyrrol-3-yl]-3,5-dihydroxyheptanoate Chemical compound CC1=C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C(C)N1C1=CC=CC=C1 QKLXBIHSGMPUQS-FGZHOGPDSA-M 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- NHFAABIHBNXKDT-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;phosphane Chemical compound P.C1CN=CO1 NHFAABIHBNXKDT-UHFFFAOYSA-N 0.000 description 1
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001429 visible spectrum Methods 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/08—Copper compounds
-
- 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
- B01J31/24—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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
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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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
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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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/65031—Five-membered rings having the nitrogen atoms in the positions 1 and 2
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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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- 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
Abstract
本发明公开了一种铜(I)配位化合物及其制备方法和应用。具体而言,本发明的铜(I)配位化合物的化学式为[Cu(dmp)(R1R2C3HN2PPh3)]BF4,其中dmp为2,9‑二甲基‑1,10‑菲啰啉,R1R2C3HN2PPh3(R1=R2=H(1a);R1=H,R2=Me(1b);R1=H,R2=Ph(1c);R1=R2=Me(1d))为异‑双齿膦吡唑配体;通过对吡唑膦配体上R1,R2基团的修饰得到四种单核铜(I)配合物[Cu(dmp)(R1R2C3HN2PPh3)]BF4(R1=R2=H(2a);R1=H,R2=Me(2b);R1=H,R2=Ph(2c);R1=R2=Me(2d)),且不同修饰基团会影响配合物的结构、吸收、发射、氧化还原电位和光催化活性。该配位化合物能够在可见光照射下催化烯烃与卤代烃分子间的原子转移自由基加成反应,具有转化效率高、适用范围广、反应条件温和等特点。
Description
技术领域
本发明属于催化化学技术领域,涉及四种铜(I)配位化合物,特别是一类含有一个亚胺膦配体和一个二亚胺配体的双齿单核铜(I)配位化合物,其制备方法及用途。
背景技术
可见光介导的光催化反应可以利用阳光促进有用的化学转化,在这些反应中最常用的分子光敏剂是传统的钌或铱的多吡啶配合物。尽管具有在可见光区吸收、激发态寿命长、适当的氧化还原性质和光稳定性方面的优势,但它们的稀有性、成本高和高毒性为有机染料或地球富含的过渡金属光敏剂等替代品的发展增添了动力;并且这类有机染料依然存在其溶液弱荧光、不稳定等缺点。
近年来,有研究报道了具有两个膦噁唑啉(N^P)配体的铜(I)配合物,在光催化制氢过程中表现出高稳定性,其光催化活性超过24小时;还有研究报道了二亚胺-二异腈铜(I)配合物催化烷基烯烃与烷基卤代物的加成反应。然而,双螯合单核铜(I)配合物[Cu(N^N)(N^P)]+含有一个亚胺-膦配体和一个二亚胺配体的报道较少。
发明内容
针对上述情况,本发明的目的在于提供四种铜(I)配位化合物及其制备方法和用途。
为了实现上述目的,本发明采用如下技术方案:
一种铜(I)配位化合物,其化学式为[Cu(dmp)(R1R2C3HN2PPh3)]BF4,其中dmp为2,9-二甲基-1,10-菲啰啉,R1、R2独立的选自氢、烷基或者芳基;优选的,烷基为C1~C6的烷基,比如甲基;芳基为苯基。
本发明铜(I)配位化合物中,dmp和R1R2C3HN2PPh3作为五元螯合配体;每个铜(I)中心与一个dmp和一个R1R2C3HN2PPh中的三个N和一个P原子配位形成高度扭曲四面体。
本发明铜(I)配位化合物的晶体属于三斜晶系,空间群均为Pī,晶胞参数分别为2a: a = 10.6131(17) Å,b= 13.336(2) Å,c= 13.515(2) Å,α= 102.248(4)°, β =94.419(5)°, γ= 107.571(4)°, V= 1761.5(5) nm3,Z= 2;2b: a = 10.8101(14) Å,b=12.1918(17) Å,c= 16.312(2) Å, α= 98.412(4)°,β = 108.062(4)°,γ= 100.700(4)°,V= 1960.0(5) nm3,Z= 2;2c: a = 12.0193(3) Å,b= 18.5661(6) Å,c= 18.5678(8) Å, α=89.141(3)°,β= 72.401(3)°,γ= 75.892(3)°,V= 3822.6(2) nm3,Z= 4;2d: a = 9.5309(5) Å,b= 12.5267(7) Å,c= 16.7613(9) Å, α= 77.384(2)°,β = 74.714(2)°,γ=79.755(2)°,V= 1868.30(18) nm3,Z= 2。
本发明铜(I)配位化合物的制备方法,包括以下步骤,以邻氟碘苯、二苯基膦为原料制备(2-氟苯基)二苯基膦;然后以(2-氟苯基)二苯基膦、吡唑为原料制备双齿膦吡唑配体;再以双齿膦吡唑配体、四氟硼酸四乙腈合铜、2,9-二甲基-1,10-菲啰啉为原料制备铜(I)配位化合物。优选的,邻氟碘苯、二苯基膦在钯催化剂存在下制备(2-氟苯基)二苯基膦;(2-氟苯基)二苯基膦、吡唑在无机碱存在下制备双齿膦吡唑配体;双齿膦吡唑配体、四氟硼酸四乙腈合铜、2,9-二甲基-1,10-菲啰啉在惰性气体中制备铜(I)配位化合物;吡唑的化学式为R1R2C3H2N2,R1、R2独立的选自氢、烷基或者芳基。进一步优选的,钯催化剂为无机钯化合物;无机碱为碳酸盐;所述惰性气体选自氮气、氩气中的任意一种。
具体的,本发明铜(I)配位化合物的制备方法为如下步骤:
(1)按照邻氟碘苯∶二苯基膦∶氯化钯=1∶1∶(0.001~0.005)的摩尔比,将邻氟碘苯,二苯基膦,氯化钯加入厚壁耐压瓶中。在惰性气体氛围下,加入碱和溶剂,密闭反应容器,加热至85℃并反应24小时。反应结束后,将反应体系的温度降至室温,采用乙酸乙酯萃取,合并有机相,经干燥、过滤、减压浓缩、硅胶柱色谱纯化,得到白色固体的纯产品(2-氟苯基)二苯基膦。
(2)按照吡唑∶(2-氟苯基)二苯基膦∶碳酸铯=3∶1∶(1~5)的摩尔比,将吡唑,(2-氟苯基)二苯基膦,碳酸铯加入厚壁耐压瓶中,在惰性气体氛围下,加入溶剂,密闭反应容器,加热至180℃并反应三天。在180℃下搅拌3天。反应结束后,将反应体系的温度降至室温,采用乙酸乙酯萃取,合并有机相,经干燥、过滤、减压浓缩、硅胶柱色谱纯化,得到白色固体的纯产品双齿膦吡唑配体。
(3)按照四氟硼酸四乙腈合铜∶双齿膦吡唑配体∶2,9-二甲基-1,10-菲啰啉=1:1:1的摩尔比,先将四氟硼酸四乙腈合铜、双齿膦吡唑配体和2,9-二甲基-1,10-菲啰啉分别加入到反应容器中,在惰性气体氛围下加入溶剂配置成溶液。先将膦配体溶液滴加至铜溶液中,室温搅拌1小时后,再向其中加入2,9-二甲基-1,10-菲啰啉的溶液,室温搅拌1小时。反应结束后,将反应混合物浓缩,加入不良溶剂使其析出,经洗涤、干燥得所述的铜(I)配位化合物。
本发明中,所述惰性气体选自氮气、氩气中的任意一种;所述溶剂分别为甲苯和N,N-二甲基乙酰胺、二氯甲烷和乙腈,不良溶剂为乙醚;所述加热通过油浴锅完成反应。
本发明公开了双齿膦吡唑配体在制备所述铜(I)配位化合物中的应用以及所述铜(I)配位化合物作为原子自由基转移(ATRA)反应光催化剂的应用,具体为所述铜(I)配位化合物在光催化芳基烯烃与烷基卤代物ATRA反应中的应用。本发明首次披露了一种作为光催化剂的双螯合单核铜(I)配合物[Cu(N^N)(N^P)]+,其能够在可见光照射下催化芳基烯烃与烷基卤代物ATRA反应;本发明公开的铜(I)配位化合物在可见光区吸收强,最大吸收带边可达600nm;其还具有较长激发态寿命、适当的氧化还原性质等特点。
附图说明
图1为本发明的铜(I)配位配合物的晶体结构示意图。
实施方式
本发明铜(I)配位配合物的制备方法如下步骤:按照四氟硼酸四乙腈合铜:双齿膦吡唑配体:2,9-二甲基-1,10-菲啰啉=1:1:1的摩尔比,先将四氟硼酸四乙腈合铜、双齿膦吡唑配体和2,9-二甲基-1,10-菲啰啉分别加入到反应容器中,在惰性气体氛围下加入溶剂配置成溶液。先将膦配体溶液滴加至铜溶液中,室温搅拌1小时后,再向其中加入2,9-二甲基-1,10-菲啰啉的溶液,室温搅拌1小时。反应结束后,将反应混合物浓缩,加入不良溶剂使其析出,经洗涤、干燥得所述的铜(I)配位化合物。
在上述制备方法中,所述惰性气体选自氮气、氩气中的任意一种;所述溶剂分别为超干二氯甲烷和超干乙腈;所述不良溶剂为乙醚。
本发明双齿膦吡唑配体(1a、1b、1c、1d)、铜(I)配位化合物(2a、2b、2c、2d)的化学结构式以及反应示意如下:
下面将结合附图和具体实施例对本发明做出进一步的描述。除非另有说明,下列实施例中所使用的试剂、材料、仪器等均可通过商业手段获得。
实施例一 1-(2-(diphenylphosphanyl)phenyl)-1H-pyrazole (1a)的制备。
将吡唑(0.41 g, 6 mmol)、(2-氟苯基)二苯基膦(0.56 g, 2 mmol)和Cs2CO3(1.95g, 6 mmol)加入到35 mL厚壁压力瓶中,在氮气气氛下,加入脱气无水N,N-二甲基乙酰胺(DMA, 5 mL)。油浴180ºC搅拌3天,反应完全后,冷却至室温,用CH2Cl2(2 × 10 mL)萃取提取反应混合物,并用水(2 × 10 mL)反冲洗组合有机层,过滤蒸发。以石油醚和乙酸乙酯为洗脱剂,用闪速柱层析法对粗产物进行纯化(产量:0.05 g;产率:77%)。
所得产物的核磁数据如下:
1H NMR (400 MHz, CDCl3, ppm): δ = 7.59 (d, 1H), 7.50–7.40 (m, 3H),7.35–7.25 (m, 11H), 7.02 (dd,J= 7.3, 3.1 Hz, 1H), 6.25 (t, 1H) ;13C NMR (101MHz, CDCl3, ppm): δ = 144.6 (d,J= 21.2 Hz), 140.4, 136.6 (d,J = 11.2 Hz),134.8, 133.9 (d,J= 20.5 Hz), 131.2 (d,J= 5.3 Hz), 129.7, 128.9, 128.8, 128.6(d,J= 7.2 Hz), 128.2, 126.3 (d,J= 2.6 Hz), 106.3;31P NMR (162 MHz, CDCl3,ppm): δ = –14.5。
实施例二 1-(2-(diphenylphosphanyl)phenyl)-3-methyl-1H-pyrazole (1b)的制备。
将3-甲基吡唑(0.49 g, 6 mmol)、(2-氟苯基)二苯基膦(0.56 g, 2 mmol)和Cs2CO3(1.95 g, 6 mmol)加入到35 mL厚壁压力瓶中,在氮气气氛下,加入脱气无水N,N-二甲基乙酰胺(DMA, 5 mL)。油浴180ºC搅拌3天,反应完全后,冷却至室温,用CH2Cl2(2 × 10mL)萃取提取反应混合物,并用水(2 × 10 mL)反冲洗组合有机层,过滤蒸发。以石油醚和乙酸乙酯为洗脱剂,用闪速柱层析法对粗产物进行纯化(产量:0.04 g;产率:63%)。
所得产物的核磁数据如下:
1H NMR (400 MHz, CDCl3, ppm): δ = 7.48 (dd,J= 7.3, 3.6 Hz, 1H), 7.41(t,J= 7.0 Hz, 1H), 7.35 (t,J= 2.0 Hz, 1H), 7.33–7.21 (m, 11H), 7.01 (dd,J=6.8, 3.7 Hz, 1H), 6.03 (d,J= 2.2 Hz, 1H), 2.24 (s, 3H);13C NMR (101 MHz,CDCl3, ppm): δ = 149.7, 144.7 (d,J= 21.2 Hz), 136.8 (d,J= 10.7 Hz), 134.8,134.0 (d,J= 20.5 Hz), 133.2 (d,J= 19.9 Hz), 131.8 (d,J= 5.6 Hz), 129.6,128.8, 128.5 (d,J= 7.0 Hz), 127.8, 126.0 (d,J= 2.5 Hz), 106.2, 13.6;31P NMR(162 MHz, CDCl3, ppm): δ = –14.4。
实施例三 1-(2-(diphenylphosphanyl)phenyl)-3-phenyl-1H-pyrazole (1c)的制备。
将3-苯基吡唑(0.86 g, 6 mmol)、(2-氟苯基)二苯基膦(0.56 g, 2 mmol)和Cs2CO3(1.95 g, 6 mmol)加入到35 mL厚壁压力瓶中,在氮气气氛下,加入脱气无水N,N-二甲基乙酰胺(DMA, 5 mL)。油浴180ºC搅拌3天,反应完全后,冷却至室温,用CH2Cl2(2 × 10mL)萃取提取反应混合物,并用水(2 × 10 mL)反冲洗组合有机层,过滤蒸发。以石油醚和乙酸乙酯为洗脱剂,用闪速柱层析法对粗产物进行纯化(产量:0.05 g;产率:61%)。
所得产物的核磁数据如下:
1H NMR (400 MHz, CDCl3, ppm): δ = 7.60 (dd,J= 2.4, 1.0 Hz, 1H), 7.57–7.54 (m, 2H), 7.52 (ddd,J = 7.8, 4.0, 1.2 Hz, 1H), 7.43 (td,J = 7.7, 1.4 Hz,1H), 7.32–7.23 (m, 14H), 7.06 (ddd,J = 7.7, 3.6, 1.3 Hz, 1H), 6.62 (d,J = 2.4Hz, 1H);13C NMR (101 MHz, CDCl3, ppm):δ = 152.3, 144.7 (d,J = 21.3 Hz), 137.4(d,J = 10.7 Hz), 135.5, 134.0 (d,J = 20.3 Hz), 133.2, 133.1, 133.0, 131.8 (d,J = 3.7 Hz), 129.7, 128.7, 128.5, 128.4 (d,J = 5.9 Hz), 127.8 (d,J = 26.3Hz), 125.8, 125.0 (d,J = 2.8 Hz), 104.0;31P NMR (162 MHz, CDCl3, ppm): δ = –13.7。
实施例四1-(2-(diphenylphosphanyl)phenyl)-3,5-dimethyl-1H-pyrazole(1d)的制备。
将3,5-二甲基吡唑(0.58 g, 6 mmol)、(2-氟苯基)二苯基膦(0.56 g, 2 mmol)和Cs2CO3(1.95 g, 6 mmol)加入到35 mL厚壁压力瓶中,在氮气气氛下,加入脱气无水N,N-二甲基乙酰胺(DMA, 5 mL)。油浴180ºC搅拌3天,反应完全后,冷却至室温,用CH2Cl2(2 × 10mL)萃取提取反应混合物,并用水(2 × 10 mL)反冲洗组合有机层,过滤蒸发。以石油醚和乙酸乙酯为洗脱剂,用闪速柱层析法对粗产物进行纯化(产量:0.02 g;产率:26%)。
所得产物的核磁数据如下:
1H NMR (400 MHz, CDCl3, ppm): δ = 7.38 (dd,J= 7.6, 1.3 Hz, 1H), 7.32–7.24 (m, 12H), 7.10 (ddd,J = 7.6, 3.4, 1.2 Hz, 1H), 5.81 (s, 1H), 2.13 (s,3H), 1.97 (s, 3H);13C NMR (101 MHz, CDCl3, ppm): δ = 148.2, 143.5 (d,J = 22.3Hz), 140.3, 138.0 (d,J= 18.1 Hz), 136.5 (d,J = 11.4 Hz), 134.3, 134.0 (d,J =20.8 Hz), 129.4, 128.8, 128.7, 128.3 (d,J = 7.2 Hz), 128.1 (d,J = 2.5 Hz),105.4, 13.5, 11.7 (d,J = 4.5 Hz);31P NMR (162 MHz, CDCl3, ppm): δ = –14.2。
实施例五 [Cu(dmp)(2a)]BF4的制备。
向[Cu(CH3CN)4]BF4(0.0315 g, 0.10 mmol)的乙腈溶液(5 mL)中,加入1a(0.0328 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。在室温下搅拌反应1小时后,再向其中加入dmp (2,9-二甲基-1,10-菲罗啉) (0.0208 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。继续搅拌1小时后,得到的透明黄色溶液。反应结束后,将反应液浓缩至约5 mL。后向溶液中加入不良溶剂Et2O (20 mL),析出2a的橙色晶体,经过滤分离后,用Et2O洗涤,真空干燥(产量:0.02g;产率:36%,以Cu计算)。
熔点:226–228 °C。
质谱:理论值:599.1426;测试值:599.1426。
所得产物的核磁数据如下:
1H NMR (400 MHz,d 6 -DMSO, ppm): 8.79 (t,J= 8.1 Hz, 2H), 8.65 (s, 1H),8.24 (d,J= 16.6 Hz, 2H), 8.00 (t,J = 7.2 Hz, 2H), 7.84 (d,J = 23.3 Hz, 2H),7.57 (m, 4H), 7.46 (s, 4H), 7.29 (s, 4H), 6.98 (d,J= 29.1 Hz, 1H), 6.55 (d,J=54.3 Hz, 1H), 2.44 (s, 6H);3C NMR (101 MHz,d 6 -DMSO, ppm): δ = 157.7, 156.6,142.2, 141.7, 141.4, 141.1, 137.1, 136.3, 132.6, 132.3 (t,J= 15.2 Hz), 131.3(d,J= 38.8 Hz), 130.5, 129.7 (t,J= 36.3 Hz), 128.2 (d,J= 8.9 Hz), 126.1 (d,J=6.2 Hz), 125.5, 124.8, 124.6, 106.9, 24.9, 24.1;31P NMR (162 MHz,d 6 -DMSO,ppm): δ = –8.3。
对所得产物进行单晶X射线衍射试验,其晶体学参数如表1所示,晶体结构如图1所示。
上述数据表明,本实施例成功得到了目标产物[Cu(dmp)(2a)]BF4。
实施例六 [Cu(dmp)(2b)]BF4的制备。
向[Cu(CH3CN)4]BF4(0.0315 g, 0.10 mmol)的乙腈溶液(5 mL)中,加入1b(0.0342 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。在室温下搅拌反应1小时后,再向其中加入dmp (2,9-二甲基-1,10-菲罗啉) (0.0208 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。继续搅拌1小时后,得到的透明黄色溶液。反应结束后,将反应液浓缩至约5 mL。后向溶液中加入不良溶剂Et2O (20 mL),析出2b的橙色晶体,经过滤分离后,用Et2O洗涤,真空干燥(产量:0.02g;产率:33%,以Cu计算)。
熔点:158–163 °C。
质谱:理论值:613.1582;测试值:613.1582。
所得产物的核磁数据如下:1H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.80 (d,J=8.1 Hz, 2H), 8.59 (s, 1H), 8.26 (d,J= 8.6 Hz, 2H), 8.02 (m, 2H), 7.85 (t,J=7.2 Hz, 1H), 7.73 (s, 1H), 7.62 (t,J= 7.2 Hz, 1H), 7.52 (s, 2H), 7.44 (s,4H), 7.33–7.11 (m, 4H), 7.00 (t,J= 7.8 Hz, 1H), 6.51 (s, 1H), 2.45 (s, 6H);13CNMR (101 MHz, d 6 -DMSO, ppm): δ = 159.3, 158.2, 153.3, 142.7 (d,J= 4.4 Hz),138.8, 138.0, 136.1, 133.6 (d,J= 16.1 Hz), 132.9 (d,J= 32.4 Hz), 131.5 (d,J=7.2 Hz),131.2 (d,J= 5.5 Hz), 129.8 (d,J= 9.5 Hz), 128.2 (d,J= 4.6 Hz), 127.8(d,J= 16.5 Hz), 126.6, 126.5, 126.4, 126.2, 108.9, 26.2, 25.7, 13.5;31P NMR(162 MHz,d 6 -DMSO, ppm): δ = –11.9。
对所得产物进行单晶X射线衍射试验,其晶体学参数如表2所示,晶体结构如图1所示。
上述数据表明,本实施例成功得到了目标产物[Cu(dmp)(2b)]BF4。
实施例七 [Cu(dmp)(2c)]BF4的制备。
向[Cu(CH3CN)4]BF4(0.0315 g, 0.10 mmol)的乙腈溶液(5 mL)中,加入1c(0.0404 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。在室温下搅拌反应1小时后,再向其中加入dmp (2,9-二甲基-1,10-菲罗啉) (0.0208 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。继续搅拌1小时后,得到的透明黄色溶液。反应结束后,将反应液浓缩至约5 mL。后向溶液中加入不良溶剂Et2O (20 mL),析出2c的黄色晶体,经过滤分离后,用Et2O洗涤,真空干燥(产量:0.04g;产率:59%,以Cu计算)。
熔点:233–236 °C。
质谱:理论值:675.1739;测试值:675.1739。
所得产物的核磁数据如下:
1H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.62 (s, 1H), 8.59 (d,J= 8.3 Hz,2H), 8.10 (s, 2H), 7.86 (t,J= 7.5 Hz, 1H), 7.74 (d,J= 8.3 Hz, 3H), 7.67 (t,J=7.5 Hz, 1H), 7.49 (t,J= 7.1 Hz, 2H), 7.42 (t,J= 6.9 Hz, 4H), 7.23 (m, 4H),7.07 (t,J= 7.7 Hz, 1H), 6.88 (d,J= 2.3 Hz, 1H), 6.85 (d,J= 7.3 Hz, 2H), 6.54(t,J= 6.7 Hz, 1H), 6.22 (s, 2H), 2.30 (s, 6H);13C NMR (101 MHz, d 6 -DMSO, ppm):δ = 158.74, 158.20, 156.33, 142.93 (d,J= 11.8 Hz), 142.70, 138.39, 137.95,136.75, 133.75 (d,J= 16.0 Hz), 133.16, 132.77, 131.74, 131.42, 131.20 (d,J=6.9 Hz), 130.47, 129.76 (d,J= 9.6 Hz), 128.70, 128.27, 127.63, 127.16,126.66, 126.44, 126.22, 125.91, 107.06, 26.33, 25.72;31P NMR (162 MHz,d 6 -DMSO,ppm): δ = –11.3。
对所得产物进行单晶X射线衍射试验,其晶体学参数如表3所示,晶体结构如图1所示。
上述数据表明,本实施例成功得到了目标产物[Cu(dmp)(2c)]BF4。
实施例8:[Cu(dmp)(2d)]BF4的制备。
向[Cu(CH3CN)4]BF4(0.0315 g, 0.10 mmol)的乙腈溶液(5 mL)中,加入1d(0.0356 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。在室温下搅拌反应1小时后,再向其中加入dmp (2,9-二甲基-1,10-菲罗啉) (0.0208 g, 0.10 mmol)的CH2Cl2(5 mL)溶液。继续搅拌1小时后,得到的透明黄色溶液。反应结束后,将反应液浓缩至约5 mL。后向溶液中加入不良溶剂Et2O (20 mL),析出2d的橙色晶体,经过滤分离后,用Et2O洗涤,真空干燥(产量:0.03g;产率:48%,以Cu计算)。
熔点:220–234 °C。
质谱:理论值:627.1739;测试值:627.1740。
所得产物的核磁数据如下:
1H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.78 (d,J= 8.2 Hz, 2H), 8.24 (d,J=9.0 Hz, 2H), 8.14–7.90 (m, 3H), 7.81 (t,J= 7.4 Hz, 1H), 7.74–7.58 (m, 2H),7.58–7.47 (m, 2H), 7.45 (m, 4H), 7.33–7.08 (m, 3H), 6.95 (t,J= 7.7 Hz, 1H),6.25 (s, 1H), 2.42 (s, 4H), 2.40 (s, 2H);13C NMR (101 MHz, d 6 -DMSO, ppm): δ =159.3, 158.2, 152.5, 144.5, 142.7 (d,J = 7.1 Hz), 138.8, 138.0, 133.7 (d,J =16.4 Hz), 132.9, 132.3, 131.4 (t,J = 21.5 Hz), 130.7 (d,J = 33.7 Hz), 129.8(d,J = 9.5 Hz), 127.8 (d,J= 15.2 Hz), 126.6, 126.5, 126.4, 126.2, 108.9,26.2, 25.7, 13.5, 12.9;31P NMR (162 MHz,d 6 -DMSO, ppm): δ = –12.2。
对所得产物进行单晶X射线衍射试验,其晶体学参数如表4所示,晶体结构如图1所示。
上述数据表明,本实施例成功得到了目标产物[Cu(dmp)(2d)]BF4。
应用实施例 可见光照射下催化苯乙烯和四溴化碳的ATRA反应。
将四溴化碳(0.2 mmol)、苯乙烯(2 equiv, 0.4 mmol)、2c (1 mol%)的混合物加入10 mL的反应管中,在氮气气氛下,加入超干MeCN (1 mL)。将混合物在室温下搅拌,并用家用45 W节能灯照射24小时,用风扇冷却。反应混合物用乙酸乙酯(3 × 5 mL)提取3次,并用3 × 5 mL的水和盐水反洗,用无水Na2SO4干燥,减压浓缩至干燥。以石油醚和乙酸乙酯为洗脱剂,用闪速柱层析法对粗产物进行纯化。产率:93%(HPLC)、91%(分离)。
所得产物的核磁数据如下:
1H NMR (400 MHz, CDCl3, ppm): δ = 7.49 (d,J = 7.0 Hz, 2H), 7.37 (t,J=7.3 Hz, 2H), 7.31 (t,J = 7.2 Hz, 1H), 5.33 (dd,J = 7.7, 4.1 Hz, 1H), 4.09(qd,J = 15.6, 5.9 Hz, 2H);13C NMR (101 MHz, CDCl3, ppm): δ = 140.8, 129.0,128. 9, 128.2, 66.5, 50.1, 35.0。
无催化剂时,产物收率为11%;将上述催化剂2c替换为其他催化剂,其余一样,可见光照射下催化苯乙烯和四溴化碳的ATRA反应,产物HPLC收率如下。2a 81%;2b 87%;2d 86%;Cu(MeCN)4BF4得不到产物;fac-[Ir(ppy)3] 75%;Rhodamine 6G 12%。
本发明设计了一系列铜(I)配位化合物,其化学式为[Cu(dmp)(R1R2C3HN2PPh3)]BF4(2a-2d);通过元素分析、红外光谱和X射线衍射对这些配合物进行了表征;研究了吡唑环上R1、R2基团的变化对铜(I)配合物的晶体结构、光催化活性的影响。在这些配合物中,化合物2c溶液可见光谱中最低的能量吸收。与2a、2b和2d相比,2c在固态下显示出更低的能量发射和更长的发射寿命,ATRA反应具有最高光催化活性。因此,这些结果为研究取代基对铜配位络合物的异二元酸配体的影响提供了一个视角。
Claims (10)
1.一种铜(I)配位化合物,其特征在于:所述铜(I)配位化合物的化学式为[Cu(dmp)(R1R2C3HN2PPh3)]BF4,其中dmp为2,9-二甲基-1,10-菲啰啉,R1、R2独立的选自氢、烷基或者芳基。
2.根据权利要求1所述铜(I)配位化合物,其特征在于:所述铜(I)配位化合物的晶体属于三斜晶系,空间群均为Pī。
3.根据权利要求1所述铜(I)配位化合物,其特征在于:烷基为C1~C6的烷基;芳基为苯基。
4.权利要求1所述铜(I)配位化合物的制备方法,其特征在于:以邻氟碘苯、二苯基膦为原料制备(2-氟苯基)二苯基膦;然后以(2-氟苯基)二苯基膦、吡唑为原料制备双齿膦吡唑配体;再以双齿膦吡唑配体、四氟硼酸四乙腈合铜、2,9-二甲基-1,10-菲啰啉为原料制备铜(I)配位化合物。
5.根据权利要求4所述铜(I)配位化合物的制备方法,其特征在于:邻氟碘苯、二苯基膦在钯催化剂存在下制备(2-氟苯基)二苯基膦;(2-氟苯基)二苯基膦、吡唑在无机碱存在下制备双齿膦吡唑配体;双齿膦吡唑配体、四氟硼酸四乙腈合铜、2,9-二甲基-1,10-菲啰啉在惰性气体中制备铜(I)配位化合物;吡唑的化学式为R1R2C3H2N2,R1、R2独立的选自氢、烷基或者芳基。
6.根据权利要求5所述铜(I)配位化合物的制备方法,其特征在于:钯催化剂为无机钯化合物;无机碱为碳酸盐;所述惰性气体选自氮气、氩气中的任意一种。
7.一种双齿膦吡唑配体,其特征在于:所述双齿膦吡唑配体的化学式为R1R2C3HN2PPh3,其中R1、R2独立的选自氢、烷基或者芳基。
8.权利要求7所述双齿膦吡唑配体的制备方法,其特征在于:以邻氟碘苯、二苯基膦为原料制备(2-氟苯基)二苯基膦;然后以(2-氟苯基)二苯基膦、吡唑为原料制备双齿膦吡唑配体。
9.权利要求7所述双齿膦吡唑配体在制备权利要求1所述铜(I)配位化合物中的应用。
10.权利要求1所述铜(I)配位化合物作为ATRA反应光催化剂的应用。
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