CN117924328A - Metal oxygen cluster compound of boropyrazole ligand, and preparation method and application thereof - Google Patents
Metal oxygen cluster compound of boropyrazole ligand, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117924328A CN117924328A CN202211321324.6A CN202211321324A CN117924328A CN 117924328 A CN117924328 A CN 117924328A CN 202211321324 A CN202211321324 A CN 202211321324A CN 117924328 A CN117924328 A CN 117924328A
- Authority
- CN
- China
- Prior art keywords
- boropyrazole
- ligand
- cluster
- compound
- metalloxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 88
- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title description 6
- 239000001301 oxygen Substances 0.000 title description 6
- 229910052760 oxygen Inorganic materials 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000004729 solvothermal method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 6
- -1 for example Chemical compound 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000002178 crystalline material Substances 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006053 organic reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 11
- CKNFSYYUVBCANI-UHFFFAOYSA-N N1N=CC=C1.[B] Chemical compound N1N=CC=C1.[B] CKNFSYYUVBCANI-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 241000239226 Scorpiones Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000006362 organocatalysis Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- KNXQDJCZSVHEIW-UHFFFAOYSA-N (3-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC(F)=C1 KNXQDJCZSVHEIW-UHFFFAOYSA-N 0.000 description 1
- NOIXNOMHHWGUTG-UHFFFAOYSA-N 2-[[4-[4-pyridin-4-yl-1-(2,2,2-trifluoroethyl)pyrazol-3-yl]phenoxy]methyl]quinoline Chemical compound C=1C=C(OCC=2N=C3C=CC=CC3=CC=2)C=CC=1C1=NN(CC(F)(F)F)C=C1C1=CC=NC=C1 NOIXNOMHHWGUTG-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- CFQQTKABRMRKQY-UHFFFAOYSA-N C(C)(=O)OC.C1(=CC=CC=C1)[N+]#N Chemical compound C(C)(=O)OC.C1(=CC=CC=C1)[N+]#N CFQQTKABRMRKQY-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 108010074122 Ferredoxins Proteins 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012042 active reagent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- ZBJWWKFMHOAPNS-UHFFFAOYSA-N loretin Chemical compound C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 ZBJWWKFMHOAPNS-UHFFFAOYSA-N 0.000 description 1
- 229950010248 loretin Drugs 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the technical field of crystal material preparation, and particularly relates to a boron pyrazole ligand metal oxide cluster compound and a preparation method and application thereof, wherein the preparation method comprises the following steps: and mixing the reaction raw materials of metal salt, organic acid, pyrazole and solvent, and performing solvothermal reaction to obtain the metal oxide cluster compound. The method disclosed by the invention has the advantages of simple synthesis steps, high repeatability, capability of performing stable synthesis in a large quantity, low requirement on the purity of raw materials, high yield of more than 40%, capability of performing macro synthesis and convenience for mass production. The raw materials are easy to obtain, the price is low, the cost is low, and the method is beneficial to mass production. In addition, the post-treatment of the method is simple and easy, the pure-phase crystalline product can be obtained only by simple alcohol washing and separation and airing at room temperature, the pollution is less, and the method meets the green and environment-friendly requirements.
Description
Technical Field
The invention belongs to the technical field of crystal material preparation, and particularly relates to a boron pyrazole ligand metal oxide cluster compound, a preparation method and application thereof.
Background
Phenylboronic acid and derivatives thereof are an important class of compounds due to their wide application in organic synthesis, catalysis, supermolecular chemistry and material engineering. The crystalline metal clusters are clear and controllable in atomic structure, rich and various in structure types, and capable of simulating and researching metal oxides from a molecular level, and attract the attention of researchers in various fields including inorganic chemistry, organic chemistry, physical chemistry and the like.
However, phenylboronic acid clusters have been less studied than carboxylic acid metal clusters. For this reason, the development of novel metal clusters of phenylboronic acids is of great significance for the synthesis and performance studies of novel structural types.
The polypyrazolylborate ligand is an example of the oldest and most classical scorpion acid salt ligand system, which was first reported in 1967 during the early origin of the scorpion ligand class, a class of tridentate ligands containing multiple N sites, covalently tethered, of the general formula [ R nB(pz)4-n]- ] wherein r=h, alkyl or aryl, pz=pyrazole or substituted pyrazole, which has found widespread use in coordination chemistry, including bio-inorganic chemistry, homogeneous catalysis and materials science, and complexes of this class of ligands with most metals or metalloids in the periodic table of elements have been prepared today.
Since the introduction of "second generation" ligands for controlled coordination in 1986, the development of this field has entered an acceleration phase, more complexes have been developed to meet the market demands, and currently, the preparation of complexes is usually performed by first synthesizing polypyrazolylborate ligands and then chelating with metals, the development of existing polypyrazolylborate ligands is mostly achieved by multi-step organic synthesis, and some active reagents are needed in the reaction: for example, a grignard reagent is needed as a reaction intermediate to combine a benzene ring and pyrazole, the reaction process is long and complex, and the prepared complex has a single configuration.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the metal oxygen cluster compound of the boropyrazole ligand, and the preparation method and the application thereof, and the synthesis of the metal oxygen cluster compound has good repeatability, and the method is concise and efficient and meets the green environmental protection requirement.
To achieve the above object, a first aspect of the present invention provides a metalloxy cluster compound of a boropyrazole ligand, wherein the metalloxy cluster compound of the boropyrazole ligand has a molecular formula: ma (L 1)b(HL2) cN
Wherein M is selected from at least one of aluminum or transition metal, L 1、L2 are the same or different and are independently selected from boron pyrazole ligands, and N is a solvent;
a. b and c are 1 or 2 at the same time;
the boropyrazole ligand has a structure shown in formula 1:
wherein R may be ortho-, meta-or para-substituted and is selected from hydrogen, hydroxy, C1-6 alkyl, C1-6 alkoxy, amino, nitro or halogen atom.
According to an embodiment of the present invention, the method for synthesizing the boropyrazole ligand of formula 1 is as follows:
According to an embodiment of the invention, said M is selected from at least one of aluminium, iron, copper, nickel, preferably aluminium, iron, copper, for example aluminium.
According to an embodiment of the invention, the N is selected from one or more of an organic solvent, preferably N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, tetrahydrofuran, e.g. acetonitrile.
According to an embodiment of the present invention, the aluminoxy cluster of the boropyrazole ligand has the formula: [ Al 2(L1)2(HL2)2. N ].
Preferably, the ferron of the boropyrazole ligand has the formula: [ Fe (L 1)(HL2). N ].
Preferably, the copper oxo cluster of the boropyrazole ligand has a molecular formula of: [ Cu (L 1)(HL2). N ].
Wherein, L 1 and HL 2 are respectively structures formed by removing two H and one H in the coordination process of the boropyrazole ligand and the metal, and interestingly, the metal matched with the boropyrazole ligand is different from the metal matched with the boropyrazole ligand along with the different number of removed H 2 O molecules: when H 2 O of one molecule is removed, the boropyrazole ligand can only carry out in-situ mononuclear assembly with Al; boron pyrazole ligands also have universality of in situ mononuclear assembly to other metals (Fe, cu, ni, etc.) when two molecules of H 2 O are removed.
According to an embodiment of the present invention, the aluminoxy cluster of the boropyrazole ligand has a chemical formula of C 51H52Al2B4N17O4, preferably the aluminoxy cluster of the boropyrazole ligand has an Mr of 1064.27.
According to an embodiment of the invention, the aluminoxy cluster of the boropyrazole ligand is a crystalline compound.
According to an embodiment of the invention, the crystalline system of the aluminoxy cluster crystalline compound of the boropyrazole ligand is monoclinic, the space group is P-1, and the unit cell parameter a isB is/>C is/>Alpha is 100.27 DEG, beta is 97.06 DEG, gamma is 117.66 DEG, V is/>
According to an embodiment of the present invention, the aluminoxy cluster crystalline compound of a boropyrazole ligand has a spatial structure substantially as described in fig. 1.
According to an embodiment of the present invention, the aluminoxy cluster crystalline compound of a boropyrazole ligand has an X-ray powder diffraction pattern substantially as shown in fig. 2.
According to an embodiment of the present invention, the aluminoxy cluster crystalline compound of a boropyrazole ligand has a thermogravimetric analysis substantially as shown in fig. 3.
According to an embodiment of the present invention, the aluminoxy cluster crystalline compound of boropyrazole ligands has an infrared spectrum substantially as shown in fig. 4.
According to an embodiment of the present invention, the aluminoxy cluster crystalline compound of the boropyrazole ligand is a pure phase colorless bulk crystalline compound.
According to an embodiment of the invention, the aluminoxy cluster of the boropyrazole ligand has a morphology substantially as shown in fig. 5.
According to an embodiment of the invention, the aluminoxy cluster of the boropyrazole ligand is an organic-inorganic hybrid compound.
According to an embodiment of the present invention, the crystalline form of the aluminoxy cluster of the boropyrazole ligand has a symmetrical structure.
According to an embodiment of the invention, the ferredoxin compound of the boropyrazole ligand has the chemical formula C 30H28FeB2N12F2.
According to an embodiment of the invention, the ferrite clusters of the boropyrazole ligands are pure phase red bulk crystals.
According to an embodiment of the invention, the ferrite cluster compound of the boropyrazole ligand is an organic-inorganic hybrid compound.
According to an embodiment of the present invention, the crystalline form of the ferrite cluster compound of the boropyrazole ligand has a symmetrical structure.
According to an embodiment of the invention, the copper oxo-cluster of the boropyrazole ligand has the chemical formula C 30H32CuB2N12.
According to an embodiment of the invention, the copper oxide cluster of the boropyrazole ligand is a pure phase blue bulk crystalline.
According to an embodiment of the invention, the copper oxo-cluster of the boropyrazole ligand is an organic-inorganic hybrid compound.
According to an embodiment of the present invention, the crystalline state of the copper oxide cluster of the boropyrazole ligand has a symmetrical structure.
Another object of the present invention is to provide a method for preparing a metalloxy cluster of the above boropyrazole ligand, the method comprising the steps of: and mixing the reaction raw materials of metal salt, organic acid, pyrazole and solvent, and performing solvothermal reaction to obtain the metal oxide cluster compound.
According to an embodiment of the invention, the metal salt is a soluble metal salt.
According to an embodiment of the present invention, the metal salt is selected from one or more of soluble aluminum salt, soluble iron salt, and soluble copper salt.
According to an embodiment of the invention, the aluminium salt is one or more of aluminium ethoxide, aluminium tert-butoxide, aluminium isobutanol, aluminium n-butoxide, aluminium n-propoxide and aluminium isopropoxide, preferably aluminium isopropoxide.
According to an embodiment of the invention, the iron salt is at least one of ferric chloride, ferric nitrate, ferric sulfate, for example ferric chloride.
According to an embodiment of the invention, the copper salt is at least one of copper nitrate, copper chloride, copper sulphate, for example copper nitrate.
According to an embodiment of the present invention, the organic acid is at least one selected from the group consisting of a substituted or unsubstituted nitrogen-containing pentaboric acid, a substituted or unsubstituted six-membered organic aromatic ring boric acid, and preferably phenylboric acid.
According to an embodiment of the present invention, the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, tetrahydrofuran, preferably acetonitrile.
According to an embodiment of the invention, the molar ratio of the metal salt to the organic acid is 1 (0.01-3), preferably 1 (0.05-2), for example 1 (0.1-1.5).
According to an embodiment of the invention, the molar ratio of the metal salt to the pyrazole is 1 (0.01-100), preferably 1 (0.1-90), for example 1 (1-90).
According to an embodiment of the invention, the solvothermal reaction temperature is 40-160 ℃; preferably the temperature of the solvothermal reaction is from 60 to 130 ℃, further preferably the temperature of the solvothermal reaction is from 70 to 100 ℃, for example 100 ℃.
According to an embodiment of the invention, the solvothermal reaction time is 48-168 hours; preferably, the time of the solvothermal reaction is 48 to 150 hours, and more preferably, the time of the solvothermal reaction is 60 to 100 hours, for example, 50 hours, 60 hours, 72 hours, 80 hours, 90 hours, 100 hours, 110 hours, 120 hours, or any point value in a range of values consisting of any two points.
As an example, the solvothermal reaction is 120 hours or 168 hours at 80 ℃, or 72 hours or 96 hours at 100 ℃.
According to an embodiment of the invention, the method comprises the steps of:
1) Mixing metal salt, organic acid, pyrazole and solvent, and performing solvothermal reaction to prepare a mixture;
2) Washing and separating the mixture obtained after the reaction in the step 1) to obtain a bulk crystalline substance.
According to an embodiment of the invention, the solvothermal reaction is carried out under isothermal conditions, preferably isothermal reaction means a reaction at constant temperature, for example in a heating device (such as an oven) at constant temperature.
According to an embodiment of the invention, the solvothermal reaction is carried out in an atmospheric or pressure vessel, for example in a glass bottle or polytetrafluoroethylene pressure vessel.
According to an embodiment of the invention, step 2) is preceded by the further step of: the mixture was cooled to room temperature.
According to an embodiment of the invention, step 2) is followed by a step of washing the isolated crystalline material.
Preferably, the washing comprises washing the separated crystalline substance with water or alcohol, and airing at room temperature.
According to an embodiment of the present invention, the alcohol is selected from at least one of low boiling alcohols, for example, at least one of methanol, ethanol, n-propanol, or the like.
According to an embodiment of the present invention, the yield of the aluminoxy compound of the boropyrazole ligand is 30% or more, preferably 50% or more, further preferably 60% or more, for example 40%, 50%, 60%, 70%, 80%, 90% or more.
The invention also provides a metal oxygen cluster compound of the boropyrazole ligand or application of the metal oxygen cluster compound of the boropyrazole ligand prepared by the method, and the application is preferably used in the fields of ceramics, medicines, electronics and the like.
According to an embodiment of the invention, the use of the aluminoxane clusters in a nonlinear optical material, an adsorbent, or a catalyst (support).
According to an embodiment of the present invention, the aluminum oxide cluster compound is applied at a temperature of 100 ℃ or lower, for example, 80 ℃ or lower, and more preferably 70 ℃ or lower.
The invention also provides an organic reaction catalytic material, which comprises the aluminum oxide cluster compound or the aluminum oxide cluster compound of the boron pyrazole ligand prepared by the method.
According to embodiments of the present invention, the catalytic material may be used to catalyze an N-H insertion reaction between N-methylaniline and methyl phenyl diazonium acetate.
The invention also provides an organic-inorganic aluminum oxide cluster material, which comprises the aluminum oxide cluster or the aluminum oxide cluster of the boron pyrazole ligand prepared by the method.
According to an embodiment of the invention, the alumoxane cluster material comprises a nonlinear optical material, a catalyst (support), or an adsorbent.
Advantageous effects
1. According to the method for preparing the metal oxide cluster compound of the boropyrazole ligand, after the reaction raw materials are mixed, the metal oxide cluster compound of the boropyrazole can be obtained through one-step self-assembly reaction by a solvothermal synthesis method. The raw materials are easy to obtain, the price is low, the cost is low, and the method is beneficial to mass production. In addition, the post-treatment of the method is simple and easy, the pure-phase crystalline product can be obtained only by simple alcohol washing and separation and airing at room temperature, the pollution is less, and the method meets the green and environment-friendly requirements.
2. The aluminoxy cluster compound of the boropyrazole ligand prepared by the invention has better stability in air and can be used in the fields of ceramics, medicines, electronics and the like.
Drawings
FIG. 1 is a schematic diagram showing the crystal structure of the crystalline product prepared in example 1 of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of the crystalline product prepared in example 1 of the present invention; the simulation value is an X-ray powder diffraction pattern obtained by simulation according to a crystal structure; the experimental value is an X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer;
FIG. 3 is a thermogravimetric analysis of the crystalline product prepared in example 1 of the present invention;
FIG. 4 is an infrared spectrum of the crystalline product prepared in example 1 of the present invention;
FIG. 5 is a photograph of a crystalline product prepared in example 1 of the present invention;
FIG. 6 is a reaction formula of an aluminum oxide cluster a (C 51H52Al2B4N17O4) of application example 1 of the present invention in which N-H is inserted between N-methylaniline and methyl phenyl diazonium acetate;
FIG. 7 is a schematic view showing the crystal structure of in-situ Fe mononuclear generation of boropyrazole ligands in application example 2 of the present invention;
FIG. 8 is a schematic diagram showing the in-situ generation of Cu single nuclei by using the boropyrazole ligand in application example 2 of the present invention.
Detailed Description
The materials according to the invention, as well as the methods of preparation and use thereof, will be described in further detail below in connection with specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
In the following examples: the analysis of the single crystal structure uses a Metal Jet D2 single crystal diffractometer of Japanese physics; the X-ray powder diffraction uses a radiation source of Cu-K alpha rays.
Example 1
Preparation of AlO cluster A
Aluminum isopropoxide (1.47 mmol), phenylboronic acid (1.0 mmol), pyrazole 2g and acetonitrile (2 mL) are placed in a 20mL glass bottle, mixed uniformly at room temperature, the mixture is kept at constant temperature in a 100 ℃ oven for 5 days, taken out, naturally cooled to room temperature, the crystalline substance is separated and then washed by ethanol, and naturally dried in air, thus obtaining a colorless transparent bulk crystalline target product with the yield of about 50% (based on the mass of aluminum isopropoxide).
Example 2
Macro preparation of aluminum oxide cluster compound a
Aluminum isopropoxide (14.7 mmol), phenylboronic acid (10.0 mmol), pyrazole 20g and acetonitrile (20 mL) are placed in a 500mL blue cap bottle, the mixture is uniformly mixed at room temperature, the mixture is kept at constant temperature in a 100 ℃ oven for 5 days, the mixture is taken out and naturally cooled to room temperature, crystalline substances are separated, then the mixture is washed by ethanol, and the mixture is naturally dried in air, thus obtaining a colorless bulk crystalline target product.
Referring to fig. 1, which is a schematic structural diagram of the target product prepared in example 1, it can be seen from the figure that the prepared compound has 2 aluminum atoms, and the aluminum atom ring peripheral ligands are two boron pyrazole ligands with one H removed, and the two boron pyrazole ligands with one H removed are connected with the aluminum atoms.
Referring to fig. 2, the target product prepared in example 1 has an X-ray powder diffraction pattern substantially consistent with a theoretical value, which indicates that the target product has higher purity and is stable in air.
Referring to fig. 3, the results of thermogravimetric analysis of the target product prepared in example 2 show that the target product has better stability at a temperature below 100 ℃ and a higher decomposition rate at a temperature exceeding 100 ℃, so that the target product aluminum oxide cluster compound prepared in example 1 should be used as a material, the optimal temperature range of the corresponding material should be below 100 ℃, and the material may be unstable at high temperature.
Referring to FIG. 4, the Al-O cluster core of the target product aluminum oxide cluster prepared in example 1 has a vibration characteristic peak of 1000-500cm -1 and the vibration characteristic peak of the organic ligand 1750-1000cm -1, which are consistent with the structure shown in FIG. 1.
Referring to fig. 5, the aluminum oxide cluster compound a prepared in example 1 is colorless bulk crystalline.
The target product prepared in the embodiment 2 is completely the same as the target product prepared in the embodiment 1, so that the macro preparation method for preparing the aluminum oxide cluster compound a is simple and easy to operate, and only the feeding amount is required to be enlarged in proportion, thereby being convenient for large-scale production.
The crystal parameters of the crystalline substance of boropyrazole aluminum oxide cluster compound a prepared in example 1 are shown in table 1:
TABLE 1 Crystal parameters of aluminum oxide cluster a in example 1
Application example 1
Application of aluminum oxide cluster compound in organic catalysis
1Mmol of the aluminum oxide cluster compound a crystal prepared in example 2 was taken, ultrasonically dispersed in 10ml of dichloromethane solvent, and 0.2 mmolN-methylaniline and 0.4mmol of phenyl diazonium methyl acetate were added to react at 80℃for 17 hours to obtain 33.3mg of the product with a yield of 65%.
Fig. 6 shows the chemical reaction formula of the present example, and it can be seen that the aluminoxane cluster compound a prepared in example 2 can be used for the reaction of organocatalytic N-H intercalation, has a yield of 65%, and can be used as a potential organocatalytic crystalline material.
Application example 2
Application of pyrazole thermal in-situ growth boron pyrazole ligand in other metals
FeCl 3 (1.00 mmol), 3-F-phenylboronic acid (1.0 mmol), pyrazole 2g and acetonitrile (2 mL) are placed in a20 mL glass bottle, the mixture is uniformly mixed at room temperature, the mixture is kept at constant temperature in a 100 ℃ oven for 5 days, taken out, naturally cooled to room temperature, the crystalline substance is separated, then washed by ethanol, and naturally dried in air, thus obtaining the red transparent blocky crystalline target product. The yield was about 50% (based on the mass of FeCl 3) and the structure is shown in FIG. 7.
Cu (NO 3)2 (1.00 mmol), phenylboronic acid (1.0 mmol), pyrazole 2g and acetonitrile (2 mL) are placed in a 20mL glass bottle, mixed uniformly at room temperature, the mixture is kept at constant temperature in a 100 ℃ oven for 5 days, taken out, naturally cooled to room temperature, the crystalline substance is separated, then washed by ethanol and naturally dried in air, and the blue transparent bulk crystalline target product is obtained, wherein the yield is about 31% (based on the mass of Cu (NO 3)2) and the structure is shown in figure 8.
Referring to fig. 7 and 8, it can be seen that the ligand is universal for in situ generation of metal mononuclei.
The foregoing description of the specific embodiments of the present invention has been presented by way of example. The scope of the invention is not limited to the exemplary embodiments described above. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention should be included in the scope of protection of the claims of the present invention.
Claims (10)
1. A metalloxy cluster of a boropyrazole ligand, characterized in that the metalloxy cluster of the boropyrazole ligand has the formula: ma (L 1)b(HL2) cN, wherein M is selected from at least one of aluminum or transition metals, L 1、L2, which are the same or different, are independently selected from boropyrazole ligands, and N is a solvent; a. b and c are 1 or 2 at the same time;
the boropyrazole ligand has a structure shown in formula 1:
wherein R may be ortho-, meta-or para-substituted and is selected from hydrogen, hydroxy, C1-6 alkyl, C1-6 alkoxy, amino, nitro or halogen atom.
2. The metalloxy cluster of boropyrazole ligands according to claim 1, wherein the method of synthesizing the boropyrazole ligands of formula 1 is as follows:
Preferably, M is at least one selected from the group consisting of aluminum, iron, copper, and nickel, preferably aluminum, iron, and copper, for example, aluminum.
Preferably, the N is selected from an organic solvent, preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, tetrahydrofuran.
3. The metalloxy cluster of boropyrazole ligands according to claim 1 or 2, characterized in that the aluminoxy cluster of boropyrazole ligands has the formula: [ Al 2(L1)2(HL2)2. N ].
Preferably, the iron cluster compound of the boropyrazole ligand has a molecular formula of: [ Fe (L 1)(HL2). N ].
Preferably, the copper cluster compound of the boropyrazole ligand has a molecular formula of: [ Cu (L 1)(HL2). N ].
4. A metalloxy cluster of a boropyrazole ligand according to claim 3, wherein the boropyrazole ligand has a formula of C 51H52Al2B4N17O4, preferably the boropyrazole ligand has an Mr of 1064.27.
Preferably, the aluminoxy cluster of the boropyrazole ligand is a crystalline compound.
Preferably, the crystalline system of the aluminoxy cluster compound of the boropyrazole ligand is monoclinic system, the space group is P-1, and the unit cell parameter a isB is/>C is/>Alpha is 100.27 degrees, beta is 97.06 degrees, gamma is 117.66 degrees and V is
Preferably, the iron cluster of the boropyrazole ligand has a chemical formula of C 30H28FeB2N12F2, preferably the iron cluster of the boropyrazole ligand is a crystalline compound.
Preferably, the copper cluster compound of the boropyrazole ligand has a chemical formula of C 30H32CuB2N12, preferably the copper cluster compound of the boropyrazole ligand is a crystalline compound.
5. A process for the preparation of a metalloxy cluster of a boropyrazole ligand according to any one of claims 1 to 4, comprising the steps of: and mixing the reaction raw materials of metal salt, organic acid, pyrazole and solvent, and performing solvothermal reaction to obtain the metal oxide cluster compound.
Preferably, the metal salt is a soluble metal salt, for example, the metal salt is one or more selected from soluble aluminum salt, soluble iron salt and soluble copper salt.
Preferably, the organic acid is at least one selected from the group consisting of a substituted or unsubstituted nitrogen-containing pentaboric acid and a substituted or unsubstituted six-membered organic aromatic ring boric acid, preferably phenylboric acid.
Preferably, the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, tetrahydrofuran and combinations thereof.
6. The process for the preparation of a metalloxy cluster of a boropyrazole ligand according to claim 5, wherein the molar ratio of the metal salt to the organic acid is 1 (0.01-3), preferably 1 (0.05-2).
Preferably, the molar ratio of the metal salt to the pyrazole is 1 (0.01-100), preferably 1 (0.1-90).
According to an embodiment of the invention, the solvothermal reaction temperature is 40-160 ℃; preferably the temperature of the solvothermal reaction is from 60 to 130 ℃, further preferably the temperature of the solvothermal reaction is from 70 to 100 ℃, for example 100 ℃.
Preferably, the solvothermal reaction time is 48-168 hours; preferably the solvothermal reaction time is from 48 to 150 hours.
7. A process for the preparation of a metalloxy cluster of a boropyrazole ligand according to claim 5 or 6, comprising the steps of:
1) Mixing metal salt, organic acid, pyrazole and solvent, and performing solvothermal reaction to prepare a mixture;
2) Washing and separating the mixture obtained after the reaction in the step 1) to obtain a bulk crystalline substance.
Preferably, the solvothermal reaction is carried out under isothermal conditions.
Preferably, step 2) is followed by a step of washing the isolated crystalline material.
8. Use of a metallothione of a boropyrazole ligand according to any one of claims 1 to 4 or prepared by a process according to any one of claims 5 to 7, preferably in the fields of ceramics, medicine, electronics and the like.
Preferably, the use of the aluminoxane clusters in a nonlinear optical material, an adsorbent, or a catalyst (support).
Preferably, the aluminum oxide cluster is applied at a temperature of 100 ℃ or less, for example, 80 ℃ or less.
9. An organic reaction catalytic material comprising a metalloxy cluster of a boropyrazole ligand according to any one of claims 1 to 4 or an aluminoxy cluster of a boropyrazole ligand prepared by the method according to any one of claims 5 to 7.
Preferably, the catalytic material may be used to catalyze an N-H intercalation reaction between N-methylaniline and methyl phenyl diazonium acetate.
10. An organic-inorganic aluminoxy cluster material comprising a metalloxy cluster of a boropyrazole ligand according to any one of claims 1 to 4 or an aluminoxy cluster of a boropyrazole ligand prepared by the method according to any one of claims 5 to 7.
Preferably, the alumoxane cluster material comprises a nonlinear optical material, a catalyst (support), or an adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211321324.6A CN117924328A (en) | 2022-10-26 | 2022-10-26 | Metal oxygen cluster compound of boropyrazole ligand, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211321324.6A CN117924328A (en) | 2022-10-26 | 2022-10-26 | Metal oxygen cluster compound of boropyrazole ligand, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117924328A true CN117924328A (en) | 2024-04-26 |
Family
ID=90763526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211321324.6A Pending CN117924328A (en) | 2022-10-26 | 2022-10-26 | Metal oxygen cluster compound of boropyrazole ligand, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117924328A (en) |
-
2022
- 2022-10-26 CN CN202211321324.6A patent/CN117924328A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9067957B2 (en) | Metal nickel-imidazolate chiral nano clathrate complex and preparation method thereof | |
| CN114195827B (en) | Carboxyl substituted ruthenium complex and preparation method and application thereof | |
| CN100545090C (en) | A kind of preparation method of X type zeolite molecular sieve | |
| CN101830918B (en) | Synthetic method of polynitrogen azole zinc/cadmium framework material | |
| CN109912809B (en) | Non-noble metal-metal organic framework composite material, preparation method and application thereof | |
| CN103626788A (en) | Hybrid material with function of adsorbing and desorbing iodine and synthetic methods thereof | |
| CN110305330B (en) | To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof | |
| CN109970719A (en) | A kind of metal-organic framework materials and preparation method and applications that the alkali based on Pyrazole Ligands is stable | |
| Huang et al. | A novel copper framework with amino tridentate N‐donor ligand as heterogeneous catalyst for ring opening of epoxides | |
| CN117924328A (en) | Metal oxygen cluster compound of boropyrazole ligand, and preparation method and application thereof | |
| CN109970985A (en) | A kind of method of room temperature synthesis metal-organic framework material PCN-224 | |
| CN113617391B (en) | Uranium polyacid crystal and preparation method and application thereof | |
| CN113956493B (en) | Non-alkyl tin oxygen cluster compound and synthetic method and application thereof | |
| Huang et al. | Hydrotris (3, 4-diphenyl-5-methylpyrazol-1-yl) borate: Control of coordination number via an equatorial substituent | |
| CN113957461A (en) | Electrochemical synthesis method of 1,1' -binaphthyl compound | |
| CN107417741B (en) | Diethylenetriamine vanadium (III)-tungsten (VI)-vanadium (IV)-oxygen cluster compound and its synthetic method | |
| Liu et al. | A novel heterospin polynuclear complex containing both macrocyclic and imino nitroxide radical ligands:{[CuL (H 2 O)](CuL) Mn (IM-2Py)}{[CuL (MeOH)](CuL) Mn (IM-2Py)}(ClO 4) 4· MeOH | |
| CN114315594B (en) | Method for catalytically synthesizing chiral amine compound by using rhodium complex | |
| CN114534790B (en) | Germanium tungsten oxy-acid salt with efficient Lewis acid-base synergistic catalytic performance | |
| CN108906116A (en) | It is a kind of for synthesizing the catalyst and preparation method and application of 2- methyl triethylene diamine | |
| CN117659071A (en) | Copper-doped aluminum oxide cluster layered material and preparation method and application thereof | |
| CN109535206A (en) | A kind of nickel complex and preparation method thereof based on phenylenediacetic Acid and 2-methylimidazole ylidene ligands | |
| CN107986990A (en) | A kind of preparation method of stratiform carbodiimides nickel compound | |
| Nestor et al. | Polyhedral organoiridaazaborane chemistry. The preparation of the eleven-vertex nido compound [9-Cl-8-(η 5-C 5 Me 5)-nido-8, 7-IrNHB 9 H 10] and its characterization by single-crystal X-ray diffraction analysis and nuclear magnetic resonance spectroscopy | |
| CN106117251B (en) | A kind of copper complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |