CN109942604B - Macrocyclic pentacoordinate copper (II) complex containing sulfur-sulfur bond and in-situ synthesis method thereof - Google Patents
Macrocyclic pentacoordinate copper (II) complex containing sulfur-sulfur bond and in-situ synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a macrocyclic penta-coordinated copper (II) complex containing sulfur-sulfur bonds and an in-situ synthesis method thereof, wherein the macrocyclic penta-coordinated copper (II) complex has a chemical formula of [ Cu (H)4L1)Cl]Cl·H2O, wherein H4L1Is a macrocyclic ligand formed by two 3, 3' -bis (5-mercapto-1, 2, 4-triazole) through a sulfur-sulfur bond. The in-situ synthesis method of the complex comprises the following steps: (1) weighing 0.04-0.05g of 3, 3' -bis (5-mercapto-1, 2, 4-triazole) and 0.03-0.04g of copper chloride dihydrate CuCl2·2H2O, mixing in 7-9mL of dimethylformamide, and stirring the mixed solution at room temperature for reaction for 6-7 h; (2) and filtering the mixed solution to obtain a green solution, placing the filtrate in a beaker, and naturally volatilizing at room temperature to obtain the single-crystal-grade green flaky crystal. The macrocyclic pentacoordinate copper (II) complex containing the sulfur-sulfur bond has potential application value in the aspects of antibiosis, tumor resistance, drug targeting release carrier and the like, and the method has wide application prospect in the aspect of in-situ synthesis of the macrocyclic metal complex containing the sulfur-sulfur bond.
Description
Technical Field
The invention relates to a copper complex, in particular to a macrocyclic pentacoordinate copper (II) complex containing sulfur-sulfur bonds and an in-situ synthesis method thereof.
Background
In situ reactions are one of the hot spots in coordination chemistry research. At present, although there are many reports on in-situ reaction, no report is found on formation of a penta-coordinated Cu (II) complex by oxidizing 3, 3' -bis (5-mercapto-1, 2, 4-triazole) into a macrocyclic dimeric ligand containing a sulfur-sulfur bond.
The sulfur-containing triazole serving as an intermediate is widely applied to the fields of medicines, pesticides and the like, and a complex formed by the sulfur-containing triazole and metal ions also has good antibacterial and anticancer activities. When the compound containing the sulfur-sulfur bond reaches tumor cells, the bond breaking reaction of the sulfur-sulfur bond can be generated due to a large amount of glutathione in the cells, so that the macrocyclic complex containing the sulfur-sulfur bond generated by oxidizing 3, 3' -bis (5-mercapto-1, 2, 4-triazole) can be used as a potential drug targeting release carrier.
Disclosure of Invention
In order to obtain a novel macrocyclic complex containing sulfur-sulfur bonds, the invention provides a macrocyclic pentacoordinate copper (II) complex containing sulfur-sulfur bonds on one hand and 3, 3' -bis (5-mercapto-1, 2, 4-triazole) (H) on the other hand4L) is used as the raw material.
The chemical formula of the macrocyclic penta-coordinated copper (II) complex containing the sulfur-sulfur bond is shown in the specification [ Cu (H)4L1)Cl]Cl·H2O, wherein H4L1Is a macrocyclic ligand formed by two 3, 3' -bis (5-mercapto-1, 2, 4-triazole) through a sulfur-sulfur bond, H4L1The structural formula is as follows:
the crystal of the macrocyclic pentacoordinate copper (II) complex containing the sulfur-sulfur bond belongs to a monoclinic system,P21/cspace group, Z = 4, unit cell parameters:a =11.679(4) Å，b =12.052(4) Å，c = 14.887(4)Å,α= 90.00 °,β= 118.28（2）°,γ= 90.00 °,V =1845.3(11)Å3。
the in-situ synthesis method of the macrocyclic pentacoordinate copper (II) complex containing the sulfur-sulfur bond comprises the following steps:
(1) weighing 0.04-0.05g of 3, 3' -bis (5-mercapto-1, 2, 4-triazole) (H)4L) and 0.03 to 0.04g of copper chloride dihydrate CuCl2·2H2O, mixing in 7-9mL of Dimethylformamide (DMF), and stirring the mixed solution at room temperature for reaction for 6-7 h;
(2) and filtering the mixed solution to obtain a green solution, placing the filtrate in a beaker, and naturally volatilizing at room temperature to obtain the single-crystal-grade green flaky crystal.
In the reaction process of the macrocyclic pentacoordinate copper (II) complex containing sulfur-sulfur bonds, the protoligand 3, 3' -bis (5-mercapto-1, 2, 4-triazole) (H)4The sulfydryl in L) is oxidized by oxygen in the air, and two pairs of sulfur-sulfur bonds are generated by end-to-end connection3, 3' -di (5-mercapto-1, 2, 4-triazole) to form a macrocyclic ligand (H)4L1) And then reacts with copper ions to generate macrocyclic pentacoordinate Cu (II) complexes.
The macrocyclic pentacoordinate copper (II) complex containing the sulfur-sulfur bond has potential application value in the aspects of antibiosis, tumor resistance, drug targeting release carrier and the like, and the method has wide application prospect in the aspect of in-situ synthesis of the macrocyclic metal complex containing the sulfur-sulfur bond.
Drawings
FIG. 1 is a schematic representation of the molecular structure of an example macrocyclic pentacoordinated copper (II) complex containing a sulfur-sulfur bond.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Examples
An in-situ synthesis method of macrocyclic pentacoordinate copper (II) complexes containing sulfur-sulfur bonds comprises the following steps:
(1) weighing 0.0400g of 3, 3' -bis (5-mercapto-1, 2, 4-triazole) (H)4L) and 0.0342g of copper chloride dihydrate CuCl2·2H2O, mixing in 8mL of Dimethylformamide (DMF), and stirring the mixed solution at room temperature for reacting for 6 hours;
(2) and filtering the mixed solution to obtain a green solution, placing the filtrate in a beaker, and naturally volatilizing at room temperature to obtain the single-crystal-grade green flaky crystal.
Referring to FIG. 1, a molecular structure diagram of a macrocyclic pentacoordinate copper (II) complex containing a sulfur-sulfur bond is shown in the example, in which external chloride ion Cl is removed for easy observation-And a crystalline water molecule. As is obvious from the figure, the inner boundary of the complex is formed by a copper ion Cu2+A chloride ion Cl-And a macrocyclic ligand (H)4L1) And (4) forming. Cu2+The ion coordinates four N atoms (N1, N4, N7, N10) of the macrocyclic ligand and a chloride ion (Cl 1) to form a modified CuN4Cl quadrangular pyramid structure, wherein Cl is positioned at the top end of the quadrangular pyramid.
Examples crystal structure determination of macrocyclic pentacoordinate copper (ii) complexes containing sulphur-sulphur bonds:
selecting cluster compound single crystals with proper size and shape, placing the cluster compound single crystals on a Supernova single crystal diffractometer, and adopting graphite to monochromate Mo-KαRadiation (a)λ= 0.71073A). Under the condition of 298(2) K respectively under certain conditionsθWithin the range ofφ-ωAnd collecting diffraction points in a scanning mode for structural analysis and correction. The non-hydrogen atoms are solved by a direct method, and the coordinates and the anisotropic thermal parameters of the non-hydrogen atoms are corrected by a full matrix least square method. Mixed hydrogenation, wherein hydrogen atoms adopt isotropic thermal parameters; non-hydrogen atoms adopt anisotropic thermal parameters. Resolution of the crystal structure and structural modification were accomplished by the SHELX-97 (Sheldrick, 1990) and SHELXL-97 (Sheldrick, 1997) packages, respectively. The data on the crystallographic and structural modifications are shown in Table 1.
TABLE 1 crystallography and Structure correction data for penta-coordinated macrocyclic Cu (II) complexes
Claims (1)
1. An in-situ synthesis method of macrocyclic pentacoordinate copper (II) complexes containing sulfur-sulfur bonds is characterized by comprising the following steps:
(1) weighing 0.04-0.05g of 3, 3' -bis (5-mercapto-1, 2, 4-triazole) and 0.03-0.04g of copper chloride dihydrate CuCl2·2H2O, mixing in 7-9mL of dimethylformamide, and stirring the mixed solution at room temperature for reaction for 6-7 h;
(2) filtering the mixed solution to obtain a green solution, placing the filtrate in a beaker, and naturally volatilizing at room temperature to obtain single-crystal-grade green flaky crystals;
the chemical formula of the macrocyclic pentacoordinate copper (II) complex is [ Cu (H)4L1)Cl]Cl·H2O, wherein H4L1Two 3, 3' -bis (5-mercapto-1, 2, 4-triazole) macrocyclic ligands formed by sulfur-sulfur bonds;
the macrocyclic pentacoordinate copper (II) complex crystal belongs to monoclinicA crystal system of a silicon-containing compound,P21/cspace group, Z = 4, unit cell parameters:a =11.679(4) Å，b =12.052(4) Å，c = 14.887(4)Å,α = 90.00 °,β = 118.28（2）°,γ = 90.00 °,V =1845.3(11)Å3。
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