CN112625067B - Nickel-based complex containing PNP and ddtc ligand coordination, and preparation method and application thereof - Google Patents
Nickel-based complex containing PNP and ddtc ligand coordination, and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 37
- 239000003446 ligand Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 206010005003 Bladder cancer Diseases 0.000 claims abstract description 6
- 208000007097 Urinary Bladder Neoplasms Diseases 0.000 claims abstract description 6
- 201000005112 urinary bladder cancer Diseases 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- -1 hexafluorophosphate Chemical compound 0.000 claims description 9
- 210000004027 cell Anatomy 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002246 antineoplastic agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 210000004881 tumor cell Anatomy 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010411 electrocatalyst Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229950004394 ditiocarb Drugs 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 206010028980 Neoplasm Diseases 0.000 abstract description 3
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000002198 insoluble material Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229940041181 antineoplastic drug Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- DQLATGHUWYMOKM-UHFFFAOYSA-L cisplatin Chemical compound N[Pt](N)(Cl)Cl DQLATGHUWYMOKM-UHFFFAOYSA-L 0.000 description 2
- 229960004316 cisplatin Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 108010020056 Hydrogenase Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012737 fresh medium Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 210000000130 stem cell Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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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
- B01J31/1845—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 phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
The invention discloses a nickel-based complex containing PNP and ddtc ligand coordination, a preparation method and application thereof, wherein the nickel-based complex has a structure shown in the figure:
the preparation method comprises the following steps: nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]Reacting with equivalent diethyl dithiocarbamic acid sodium salt under mild condition, and obtaining the target product simply, rapidly and with high yield. The nickel-based complex disclosed by the invention has excellent electrocatalytic hydrogen release performance, strong toxicity to bladder cancer cells, and good application prospects in the fields of hydrogen energy and tumor treatment.
Description
Technical Field
The invention relates to the technical fields of chemistry, energy, pharmaceutical chemistry, medicine and the like. More particularly, the invention relates to a nickel-based complex containing PNP and ddtc ligand coordination, and a preparation method and application thereof.
Background
The traditional fossil energy sources have limited reserves and are difficult to regenerate, so that the environment is polluted to a certain extent, and people are forced to search for new sustainable green energy sources to replace fossil energy sources. The hydrogen energy source is widely interesting to scientists because of the advantages of high combustion heat value, high energy density, green environment protection, recycling and the like. The key to hydrogen energy development is the hydrogen production catalyst. Noble metal-based catalysts, although highly catalytic, have low levels of noble metals in the crust and are expensive, limiting their use on a large scale. Searching for inexpensive, efficient catalysts is a hotspot problem in hydrogen energy development. The hydrogenase existing in the nature can efficiently catalyze and produce hydrogen without overpotential, and lays a foundation for the development of bionic hydrogen production catalysts. There is a literature report (inorg.chim. Acta,2020,507,119587) that a nickel-based catalyst containing nitrogen-doped bidentate phosphine ligand (PNP) and disulfide ligand can effectively electro-catalyze proton reduction to produce hydrogen, and the catalytic current ratio (ica/ipa) can reach 44-55 times. On the other hand, there are literature reports (chem. Commun.,2012,48,4450-4452; coord. Chem. Rev.,2014,270-271,127-150) that bases overhanging the periphery of the metal center can assist proton transfer, promote proton-electron coupled transfer effect (PCET) and improve catalytic efficiency. The invention provides a novel nickel-based complex containing PNP and ddtc ligand coordination and high-efficiency electrocatalytic hydrogen production effect by introducing a nitrogen-containing diethyl dithiocarbamate (ddtc) ligand.
In addition, there are reports (chem. Eur. J.,2017,23,9674-9682) that nickel-based complexes containing polypyridine and ddtc ligands can effectively kill tumor cells and even tumor stem cells. The invention also provides and discovers the toxicity of the novel nickel-based complex containing PNP and ddtc ligand coordination to bladder cancer cells (RT 112), has better drug effect than commercial cisplatin drugs, and has good application prospect in anti-tumor drug research.
Disclosure of Invention
It is an object of the present invention to provide a nickel-based complex containing PNP and ddtc ligands coordinated and a method for preparing the same.
It is another object of the present invention to provide a novel nickel-based complex containing PNP and ddtc ligands coordinated as an electrocatalyst for the electro-reduction of proton hydrogen.
It is still another object of the present invention to provide a novel nickel-based complex containing PNP and ddtc ligands coordinated for use as an antitumor agent.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a nickel-based complex containing PNP and ddtc ligands coordinated, having a structure as shown in formula (1):
wherein the substituent R groups are n-hexyl, cyclohexyl, phenyl and benzyl.
The invention also provides a preparation method of the nickel-based complex containing PNP and ddtc ligand coordination, which comprises the following steps:
step (1): nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]Dissolving in a solvent;
step (2): sodium diethyldithiocarbamate (Na (ddtc). 3H 2 O) dissolving in a solvent;
step (3): slowly dropwise adding Na (ddtc) solution in step (2) to [ Ni (L) in step (1) under continuous stirring PNP )Cl 2 ]In the solution, carrying out reaction under set conditions;
step (4): removing the solvent in the step (3), adding an acetone solvent for dissolution, and filtering to remove sodium chloride; and adding hexafluorophosphate, stirring for 10 minutes, and adding distilled water until the product is separated out.
Preferably, the solvent in the step (1) is dichloromethane, acetone or methanol, and the PNP-coordinated nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]The concentration is 0.01 to 0.1 mol per liter; the solvent in the step (2) is acetone or methanol, and the Na (ddtc) concentration is 0.02-0.2 mol/L.
Preferably, in the step (3), PNP-coordinated nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]And Na (ddtc) is 1 to 1, and the conditions are specifically: the reaction temperature is room temperature, the reaction time is 1-2 hours, and the reaction atmosphere is air.
Preferably, the hexafluorophosphate in the step (4) is potassium, sodium or ammonium salt, and the molar amount is PNP-coordinated nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]3 to 5 times of the total weight of the steel sheet.
The invention also provides an application of the nickel-based complex containing PNP and ddtc ligand coordination in catalytic hydrogen production, in particular to an application of the nickel-based complex serving as an electrocatalyst in electro-reduction proton hydrogen desorption under a weak acid condition, wherein the weak acid is acetic acid.
The invention also provides an application of the nickel-based complex containing PNP and ddtc ligand coordination as an anti-tumor drug, wherein the tumor cell is a bladder cancer cell line RT112.
The invention at least comprises the following beneficial effects:
the nickel-based complex containing PNP and ddtc ligand coordination is simple and convenient in preparation method, can be used as a hydrogen production catalyst, has a high electrocatalytic reduction hydrogen release effect in weak acid medium, and can kill tumor cells efficiently. The invention also has the following advantages:
(1) The nickel-based complex has novel structure, simple synthesis process, mild reaction condition and high yield;
(2) The preparation method of the nickel-based complex containing PNP and ddtc ligand coordination is applicable to various PNP ligands with different R groups, and has certain universality;
(3) The nickel-based complex has proper stability, and is beneficial to storage, transportation and application;
(4) The nickel-based complex can efficiently produce hydrogen under the weak acid condition, and has potential application in hydrogen energy preparation;
(5) Such nickel-based complexes have very low values of semi-inhibitory concentration (IC 50 ) Has strong toxicity to tumor cells and good application prospect and potential in the field of tumor treatment.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound 1 provided by the invention in deuterated chloroform;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 2 provided by the present invention in deuterated dimethyl sulfoxide;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of compound 3 provided by the present invention in deuterated chloroform;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of compound 4 provided by the present invention in deuterated chloroform;
FIG. 5 is a diagram showing the structure of the cationic crystal of Compound 1 according to the present invention;
FIG. 6 is a synthetic scheme of a nickel-based complex of the present invention containing PNP and ddtc ligands coordinated.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
The experimental methods described in the following embodiments are conventional methods unless otherwise indicated, and the reagents and materials are commercially available.
The invention provides a preparation method of a nickel-based complex containing PNP and ddtc ligand coordination, and the synthetic route diagram is shown in figure 6.
Example 1
under stirring at room temperature under air atmosphere, 5mL of Na (ddtc). 3H was dissolved in 72mg 2 O in acetone was slowly added dropwise to 15mL of a solution of 189mg precursor [ Ni (Ph) 2 PN(n-hexyl)PPh 2 Cl 2 ]Is in methylene chloride solution. The reaction was stirred for 1 hour. The solvent was removed by rotary evaporation, the product was dissolved with 10mL of acetone and the insoluble material was removed by filtration. Three equivalents of sodium hexafluorophosphate were added to the filtrate and stirring was continued for 10 minutes. Finally, 20mL of distilled water is added dropwise to precipitate a product, and the product is filtered and dried to obtain 212mg (83%) of a pure product. 1 H NMR(400MHz,CDCl 3 )δ7.85–7.77(m,8H),7.77–7.70(m,4H),7.69–7.61(m,8H),3.66(q,J＝7.2Hz,4H),3.08–2.95(m,2H),1.23(t,J＝7.2Hz,6H),1.08–0.92(m,4H),0.89–0.74(m,4H),0.70(t,J＝7.3Hz,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 201.29,133.84,132.75,130.16,127.75,49.57,44.82,30.96,29.52,26.43,22.34,13.88,12.64 the nuclear magnetic hydrogen spectrum of compound 1 is shown in figure 1. The cationic crystal structure of compound 1 is shown in FIG. 5.
Example 2
under stirring at room temperature under air atmosphere, 5mL of the solution was dissolved with 13mg of Na (ddtc). 3H 2 O in acetone was slowly added dropwise to 15mL of the precursor [ Ni (Ph) 2 PN(cyclohexyl)PPh 2 Cl 2 ]Is in methylene chloride solution. The reaction was stirred for 1 hour. The solvent was removed by rotary evaporation, the product was dissolved with 10mL of acetone and the insoluble material was removed by filtration. Three equivalents of sodium hexafluorophosphate were added to the filtrate and stirring was continued for 10 minutes. Most preferably, the first to fourthThen, 20mL of distilled water was added dropwise to precipitate a product, which was filtered and dried to obtain 38.3mg (87%) of a pure product. 1 H NMR(400MHz,DMSO)δ8.03(dd,J＝13.4,6.8Hz,8H),7.80(t,4H),7.74(t,J＝7.3Hz,8H),3.62(q,J＝7.1Hz,4H),3.46–3.33(m,1H),1.36–1.22(m,5H),1.10(t,J＝7.1Hz,6H),1.01–0.86(m,2H),0.76(dd,J＝22.7,11.3Hz,2H),0.68–0.54(m,1H). 13 C NMR (101 MHz, DMSO). Delta. 199.37,133.58,132.70,130.03,128.03,62.45,44.48,32.51,24.76,12.29 the nuclear magnetic hydrogen spectrum of Compound 2 is shown in FIG. 2.
Example 3
Compound 3
Is prepared from the following steps:
under stirring at room temperature under air atmosphere, 5mL of 84mg of Na (ddtc). 3H was dissolved in 2 O in acetone was slowly added dropwise to 15mL of the solution in 210mg of precursor [ Ni (Ph) 2 PN(Ph)PPh 2 Cl 2 ]Is in methylene chloride solution. The reaction was stirred for 1 hour. The solvent was removed by rotary evaporation, the product was dissolved with 10mL of acetone and the insoluble material was removed by filtration. Three equivalents of sodium hexafluorophosphate were added to the filtrate and stirring was continued for 10 minutes. Finally, distilled water (20 mL) is added dropwise to precipitate a product, and the product is filtered and dried to obtain 228mg (79%) of a pure product. 1 H NMR(400MHz,CDCl3)δ7.78(dt,J＝8.1,4.1Hz,8H),7.73(t,J＝7.5Hz,4H),7.61(t,J＝7.6Hz,8H),7.16(t,J＝7.3Hz,1H),7.09(t,J＝7.6Hz,2H),6.51(d,J＝7.4Hz,2H),3.70(q,J＝7.2Hz,4H),1.26(t,J＝7.2Hz,6H). 13 C NMR(101MHz,CDCl 3 ) Delta 200.78,139.38,134.04,133.02,130.12,130.04,127.85,127.41,125.18,44.95,12.66 the nuclear magnetic hydrogen spectrum of compound 3 is shown in figure 3.
Example 4
Compound 4
Is prepared from the following steps:
under stirring at room temperature under air atmosphere, 5mL of Na (ddtc). 3H was dissolved in 17mg 2 O in acetone was slowly added dropwise to 15mL of the solution in 43mg of precursor [ Ni (Ph) 2 PN(CH 2 Ph)PPh 2 Cl 2 ]Is a dichloromethane solution of (2)Is a kind of medium. The reaction was stirred for 1 hour. The solvent was removed by rotary evaporation, the product was dissolved with 10mL of acetone and the insoluble material was removed by filtration. Three equivalents of sodium hexafluorophosphate were added to the filtrate and stirring was continued for 10 minutes. Finally, 20mL of distilled water is added dropwise to precipitate a product, and the product is filtered and dried to obtain 49mg (84%) of a pure product. 1 H NMR(400MHz,CDCl 3 )δ7.80–7.63(m,12H),7.58(t,J＝7.5Hz,8H),7.04(t,J＝7.5Hz,1H),6.88(t,J＝7.7Hz,2H),6.46(d,J＝7.2Hz,2H),4.25(t,J＝11.2Hz,2H),3.64(q,J＝7.2Hz,4H),1.22(t,J＝7.2Hz,6H). 13 C NMR(101MHz,CDCl 3 ) Delta 201.24,133.68,132.99,132.78,130.02,129.50,128.89,128.69,127.37,52.95,44.79,12.60 the nuclear magnetic hydrogen spectrum of compound 4 is shown in FIG. 4.
The application of the compounds 1-4 in hydrogen production by electrocatalytic reduction of protons.
0.01mmol of compounds 1-4 are dissolved in 3.5mL of acetonitrile electrolyte containing tetrabutylammonium tetrafluoroborate, a glassy carbon electrode is used as a working electrode, a silver chloride/silver electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the performance of the compounds in electrocatalytic proton reduction hydrogen release under weak acid (acetic acid) environment is tested by a three-electrode system, and the related results are shown in table 1. As can be seen from Table 1, these compounds have good electrocatalytic hydrogen desorption properties, and a catalytic current ratio i cat /i pa Can reach 58-88 times. Compared with the nitrogen-free disulfide ligand nickel-based compound (Inorg.Chim. Acta,2020,507,119587; the ratio of the ica/ipa is 44-55 times), the nitrogen-containing ddtc ligand coordinated nickel-based compound provided by the invention is more excellent.
Electrocatalytic hydrogen evolution performance of the compounds of Table 1 under proton sources of acetic acid
The compounds 1-4 are used as antitumor drugs.
Toxicity of compounds 1-4 to bladder cancer cell line RT112 cells was assessed by standard MTT method, and the general experimental procedure is as follows: RT112 is increased to 2X 10 4 Cell/well density was seeded into 96-well plates and incubated for 24 hours. The wells were divided into 8 groups of 6 wells in parallel, each group being concentrated according to the compoundThe cells were incubated with 0,1,2,5,10,20,50,100. Mu.M added to each well for 72 hours. After careful pipetting of the broth, 150. Mu.L of fresh medium and 10. Mu.L of MTT solution (5 mg/mL) were added and incubated for an additional 4 hours. The culture broth was removed, 150. Mu.L of DMSO was added, and after shaking for 10 minutes, the absorbance value per well was recorded with a microplate reader. Obtaining the semi-inhibitory concentration IC for each compound by fitting 50 The data are shown in Table 2. Compared with the traditional cisplatin medicine (IC 50 =3.5 μm, see reference inorg.chem.2019,58, 15017-159226) the present invention provides nickel-based compounds with quite even more excellent anticancer activity (2-8 fold).
TABLE 2MTT assay evaluation of half inhibitory concentration IC of Compounds 1-4 on RT112 bladder cancer cells 50 Value (mu mol/L)
| Compounds of formula (I) | 1 | 2 | 3 | 4 |
| IC 50 | 3.67 | 1.93 | 0.44 | 1.77 |
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (8)
1. A nickel-based complex containing PNP and ddtc ligands coordinated, having a structure as shown in formula (1):
wherein the substituent R groups are n-hexyl, cyclohexyl, phenyl and benzyl.
2. A process for preparing a nickel-based complex containing PNP and ddtc ligands according to claim 1, comprising the steps of:
step (1): nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]Dissolving in a solvent;
step (2): dissolving a sodium diethyldithiocarbamate in a solvent;
step (3): slowly dropwise adding Na (ddtc) solution in step (2) to [ Ni (L) in step (1) under continuous stirring PNP )Cl 2 ]In the solution, carrying out reaction under set conditions; the setting conditions are specifically as follows: the reaction temperature is room temperature, the reaction time is 1-2 hours, and the reaction atmosphere is air;
step (4): removing the solvent in the step (3), adding an acetone solvent for dissolution, and filtering to remove sodium chloride; adding hexafluorophosphate, stirring for 10 min, and adding distilled water until the product is separated out;
PNP-coordinated nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]The concrete structure is as follows: [ Ni (Ph) 2 PN(n-hexyl)PPh 2 Cl 2 ]Or [ Ni (Ph) 2 PN(cyclohexyl)PPh 2 Cl 2 ]Or [ Ni (Ph) 2 PN(Ph)PPh 2 Cl 2 ]Or [ Ni (Ph) 2 PN(CH 2 Ph)PPh 2 Cl 2 ]。
3. The method for preparing a nickel-based complex containing PNP and ddtc ligands according to claim 2, wherein the solvent in said step (1) is dichloromethane, acetone or methanol, and the PNP-containing nickel dichloride precursor [ Ni (L PNP )Cl 2 ]The concentration is 0.01 to 0.1 mol per liter; the solvent in the step (2) is acetone or methanol, and the Na (ddtc) concentration is 0.02-0.2 mol/L.
4. The method for producing a nickel-based complex containing PNP and ddtc ligand coordination according to claim 2 or 3, wherein said step (3) is performed by using a PNP-containing nickel dichloride precursor [ Ni (L PNP )Cl 2 ]And Na (ddtc) is 1 to 1.
5. The method for preparing a nickel-based complex containing PNP and ddtc ligands according to claim 4, wherein said hexafluorophosphate in said step (4) is a potassium, sodium or ammonium salt in a molar amount of PNP-containing nickel dichloride precursor [ Ni (L) PNP )Cl 2 ]3 to 5 times of the total weight of the steel sheet.
6. Use of a nickel-based complex containing PNP and ddtc ligand coordination according to claim 1 for catalytic hydrogen production, in particular as an electrocatalyst for electro-reduction proton hydrogen desorption under weak acid conditions.
7. Use of a nickel-based complex containing PNP and ddtc ligands coordinated according to claim 6, said weak acid being acetic acid, for catalytic hydrogen production.
8. The use of a nickel-based complex containing PNP and ddtc ligands as defined in claim 1 for the preparation of an antitumor agent, wherein the tumor cell is bladder cancer cell line RT112.
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