CN109912628A - A kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage and its in-situ synthetic method - Google Patents
A kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage and its in-situ synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage and its in-situ synthetic method, nickel (II) the coordination chemistry formulas are as follows: [Ni (H4L1)(H2O)2] 2Cl, wherein H4L1The macrocyclic ligand formed for two 3,3 '-two (5- sulfydryl -1,2,4- triazole) by sulphur-sulfide linkage.The in-situ synthetic method of nickel (II) complex includes the following steps: that (1) weighs 0.04-0.05g 3,3 '-two (5- sulfydryl -1,2,4- triazole) and 0.04-0.05g six and is hydrated Nickel Chloride NiCl2·6H2O is added in 3-5 mL methanol and 5-7mL Isosorbide-5-Nitrae-dioxane, and reaction 6-7 h is stirred at room temperature in mixed liquor；(2) above-mentioned mixed liquor is filtered, filtrate is placed in a beaker, volatilized naturally at room temperature, obtain monocrystalline grade purple flat crystal.Nickel (II) complex of the present invention antibacterial, it is antitumor and as drug targeting release in terms of have potential application, this method has wide application prospects in terms of the fabricated in situ of sulfur-bearing-sulfide linkage Macrocyclic metal complex.
Description
Technical field
The present invention relates to nickel complex, big ring nickel (II) complex of the dimerization of specifically a kind of sulfur-bearing-sulfide linkage and its original position
Synthetic method.
Background technique
Reaction in-situ is one of the hot spot of Coordinative Chemistry research.Though there are much document reports about reaction in-situ at present,
But it there are no 3,3 '-two (5- sulfydryl -1,2,4- triazoles) and be oxidized generation sulfur-bearing-sulfide linkage dimerization macrocyclic ligand and then shape
At the report of Ni (II) complex.
Sulfur-bearing triazole is widely used in the fields such as medicine, pesticide as intermediate, the cooperation formed with metal ion
Object also has preferable antibacterial and anticancer activity.It, can be because in cell when due to reaching tumour cell containing sulphur-sulfide linkage compound
A large amount of existing glutathione and the reaction of sulphur-sulfide linkage scission of link occurs, therefore, by 3,3 '-two (5- sulfydryl -1,2,4- triazoles)
It is oxidized the carrier that can be used as potential drug targeting release containing sulphur-sulfide linkage macrocyclic complex of generation.
Summary of the invention
In order to obtain new sulfur-bearing-sulfide linkage macrocyclic complex, one aspect of the present invention is to provide a kind of sulfur-bearing-sulfide linkage
On the other hand big ring nickel (II) complex of dimerization is also provided with 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H4It L) is raw material
The complex in-situ synthetic method.
A kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage of the present invention, chemical formula are as follows: [Ni (H4L1)
(H2O)2] 2Cl, wherein H4L1Matched for two 3,3 '-two (5- sulfydryl -1,2,4- triazole) by the big ring that sulphur-sulfide linkage is formed
Body, H4L1Structural formula is as follows:
。
Big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage of the present invention, crystal belong to anorthic system,Pī space group, Z=
2, cell parameter are as follows:a=6.972 (2),b=10.614 (3,c=13.494 (4),α=112.499 (4) °,β=
94.422 (5) °,γ=91.049 (5) °,V = 918.6(5) Å3。
The in-situ synthetic method of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage of the present invention, includes the following steps:
(1) 0.04-0.05g 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H is weighed4L) and 0.04-0.05g six is hydrated two
Nickel chloride NiCl2·6H2O is added in 3-5 mL methanol and 5-7mL Isosorbide-5-Nitrae-dioxane, and mixed liquor is stirred at room temperature instead
Answer 6-7h；
(2) above-mentioned mixed liquor is filtered, filtrate is placed in a beaker, volatilized naturally at room temperature, obtain monocrystalline grade purple sheet
Crystal.
During the reaction in-situ of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage of the present invention, first wife's body 3,3 '-two
(5- sulfydryl -1,2,4- triazole) (H4L sulfydryl) is aoxidized by the oxygen in air during the reaction, passes through head and the tail phase
Even, two pairs of sulphur-sulfide linkages are generated, by two 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H4L) ligand connects into big ring H4L1,
And then it is coordinated with nickel ion and generates macrocyclic complex.
Big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage of the present invention is in antibacterial, antitumor and release as drug targeting
Carrier put etc. has potential application, fabricated in situ of this method in sulfur-bearing-sulfide linkage Macrocyclic metal complex
Aspect has wide application prospects.
Detailed description of the invention
Fig. 1 is the schematic arrangement of big ring nickel (II) complex of embodiment sulfur-bearing-sulfide linkage dimerization.
Specific embodiment
The content of present invention is further described below with reference to embodiment, but is not limitation of the invention.
Embodiment
A kind of in-situ synthetic method of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage, includes the following steps:
(1) 0.0400g 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H is weighed4L) and 0.0475g six is hydrated Nickel Chloride
NiCl2·6H2O is added in 4mL methanol and 6mL Isosorbide-5-Nitrae-dioxane, and reaction 6h is stirred at room temperature in mixed liquor；
(2) above-mentioned mixed liquor is filtered, filtrate is placed in a beaker, volatilized naturally at room temperature, obtain monocrystalline grade purple sheet
Crystal.
Referring to Fig. 1, the schematic arrangement of big ring nickel (II) complex of embodiment sulfur-bearing-sulfide linkage dimerization, in order to just
In observation, two extraneous chloride ions are deleted.From figure it will be evident that the interior boundary of the complex is by a Ni2+, a big ring
Ligand (H4L1) and two H2O molecular composition, Ni2+Ion respectively with macrocyclic ligand (H4L1) four N atoms (N1, N4, N7,
N10) and in two water O atom (O1, O2) is coordinated, and forms the NiN of a deformation4O2Octoploids structure.Ni2+Ion and four N
The octahedral equatorial plane of atomic building, and two hydrones are respectively at the upper and lower of plane.
The crystal structure determination of big ring nickel (II) complex of embodiment sulfur-bearing-sulfide linkage dimerization:
The all proper cluster compound monocrystalline of size and shape is selected, is placed on SuperNova single crystal diffractometer, using graphite list
Color Mo-KαRadiation (λ= 0.71073 Å).Respectively certain under the conditions of 298 (2) KθIn range withφ-ωScanning side
Formula collects point diffraction, is used for structure elucidation and amendment.Non-hydrogen atom is solved with direct method, and to their coordinate and its respectively to different
Property thermal parameter corrected with complete matrix least square method.Mixed hydrogenation, hydrogen atom use isotropism thermal parameter；Non-hydrogen atom
Using anisotropy thermal parameter.The parsing of crystal structure and structural modifications respectively by SHELX-97 (Sheldrick, 1990) and
SHELXL-97 (Sheldrick, 1997) program bag is completed.1 is shown in Table in relation to crystallography and structural modifications data.
Table 1, big ring nickel (II) complex crystal and structural modifications data
Claims (3)
1. a kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage, it is characterized in that: big ring nickel (II) coordination chemistry of the dimerization
Formula are as follows: [Ni (H4L1)(H2O)2] 2Cl, wherein H4L1Pass through sulphur-for two 3,3 '-two (5- sulfydryl -1,2,4- triazole)
The macrocyclic ligand that sulfide linkage is formed.
2. big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage according to claim 1, it is characterized in that: the dimerization
Big ring nickel (II) complex, crystal belong to anorthic system,Pī space group, Z=2, cell parameter are as follows:a=6.972 (2),b
=10.614 (3,c=13.494 (4),α =112.499 (4) °,β =94.422 (5) °,γ = 91.049(5)
°,V = 918.6(5) Å3。
3. the in-situ synthetic method of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage according to claim 1, feature
It is to include the following steps:
(1) it weighs 0.04-0.05g 3,3 '-two (5- sulfydryl -1,2,4- triazole) and 0.04-0.05g six and is hydrated Nickel Chloride
NiCl2·6H2O is added in 3-5 mL methanol and 5-7mL Isosorbide-5-Nitrae-dioxane, and reaction 6-7 is stirred at room temperature in mixed liquor
h；
(2) above-mentioned mixed liquor is filtered, filtrate is placed in a beaker, volatilizees naturally at room temperature, obtains monocrystalline grade purple sheet
Crystal.
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Application publication date: 20190621 |