CN1709899A - Method for preparing binuclear tricarbonyl chrominium complex - Google Patents
Method for preparing binuclear tricarbonyl chrominium complex Download PDFInfo
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- CN1709899A CN1709899A CN 200510026729 CN200510026729A CN1709899A CN 1709899 A CN1709899 A CN 1709899A CN 200510026729 CN200510026729 CN 200510026729 CN 200510026729 A CN200510026729 A CN 200510026729A CN 1709899 A CN1709899 A CN 1709899A
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- chromium
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Abstract
This invention has disclosed a manufacturing method to binuclear tricarbonyl chromium complex. It adopts single-nuclear eta<6> tricarbonyl chromium complex as raw materials, one kind or many kinds of mixture of dioxane, tetrahydrofurans, butylether as medium, deoxidize with standard Schlenk technology, under the condition of mixing, when the temperature is 50 DEG C to 150 DEG C, sealed heating 20 to 40 hours, precipitate reaction products with petroleum ether, get binuclear tricarbonyl chromium complex finally. Production ratio of binuclear tricarbonyl chromium complex is up to 30 percent.
Description
Technical field
The present invention relates to the preparation method of inner complex of the compound of a kind of containing＞C=O base, relating to a kind of in particular is the preparation method of the binuclear tricarbonyl chrominium complex of organic ligand with carbazole and derivative thereof.
Background technology
η
6The aromatic hydrocarbons tricarbonyl chrominium complex has formed typical D-π-A structure because its tricarbonyl chromium group can interact with the aromatic ring delocalized, in many-sides such as photoelectricity, molecular designing and catalytic fields good prospects for application is arranged.Especially binuclear tricarbonyl chrominium complex owing to introduced two tricarbonyl chromium groups with strong electron-withdrawing power in the organic ligand molecule, has formed the electron resonance structure at intramolecule, and it is compared with mononuclear complex rapid raising in nature.At present, domestic and international preparation for binuclear tricarbonyl chrominium complex does not still have good method.The obtaining basically of binuclear tricarbonyl chrominium complex relies on and is extracted in that resulting micro-by product carries out in the monokaryon product building-up process, and selected organic ligand is also very limited.Because the amount of the double-core product that this kind method can access is few, leaching process also often is accompanied by than lossy, thereby makes the research application of binuclear tricarbonyl chrominium complex receive great restriction.
Summary of the invention
Technical problem to be solved by this invention provide a kind of simply, the preparation method of binuclear tricarbonyl chrominium complex efficiently, this method is an organic ligand with carbazole and derivative thereof, can synthesize a series of binuclear tricarbonyl chrominium complex.
The technical solution used in the present invention: a kind of preparation method of binuclear tricarbonyl chrominium complex, with monokaryon η
6Tricarbonyl chrominium complex is a raw material, with one or more the mixture in organic coordination solvent dioxane, tetrahydrofuran (THF) or the n-butyl ether is medium, the deoxygenation of employing standard Schlenk technology, under agitation condition, 50 ℃ of-150 ℃ of heated sealed reaction 20-40h, adopt sherwood oil that reaction product is carried out precipitate and separate at last, obtain η
6The binuclear tricarbonyl chrominium complex of trans coordination structure.
Described monokaryon η
6Tricarbonyl chrominium complex is preferred: η
6-carbazole tricarbonyl chromium, η
6-vinylcarbazole tricarbonyl chromium, η
6-ethyl carbazole tricarbonyl chromium, η
6-amino-ethyl carbazole tricarbonyl chromium, η
6-nitro-ethyl carbazole tricarbonyl chromium, η
6-3-aldehyde radical-9-ethyl carbazole tricarbonyl chromium, η
6-N-aminocarbazole tricarbonyl chromium, η
6-4-methoxyl group carbazole tricarbonyl chromium or η
6-4-hydroxycarbazole tricarbonyl chromium.
Beneficial effect of the present invention: it is raw material that the present invention adopts easy synthetic monokaryon tricarbonyl chrominium complex, the reaction conditions gentleness, and the operability height, the productive rate of binuclear tricarbonyl chrominium complex is up to 30%.The mechanism of the synthetic binuclear tricarbonyl chrominium complex of the present invention may be: encircle more condensed aromatics because of have planar conjugate electron rich ring can be used as electron donor(ED) (D) can with electron acceptor(EA) (A) Cr (CO) 3 formation D-π-A type structural molecule.This metal-big π the key of aromatic hydrocarbons conjugation diagram of system reveals very strong πDian Zi delocalization, can cause intramolecular charge transfer, and makes the coordination of Cr (CO) 3 groups between intramolecularly and intermolecular different kinds of aromatic ring move rearrangement IRHRs under the appropriate solvent effect.Simultaneously, according to the single crystal structure plane equation shows, in the binuclear tricarbonyl chrominium complex Cr atom to aromatic ring planar vertical range less than corresponding monokaryon tricarbonyl chrominium complex.It is higher that the binuclear tricarbonyl chrominium complex that above-mentioned reaction mechanism is indicating part of the same race and mononuclear complex are compared stability, thereby also might move transformation by the coordination of tricarbonyl chromium group in theory and obtain its product.In fact, the method applied in the present invention, just based on above-mentioned mechanism, the monokaryon tricarbonyl chrominium complex is dissolved in the dioxane equal solvent, make the tricarbonyl chromium group under suitable temperature of reaction, absorb energy, coordination effect by solvent simultaneously overcomes the rearrangement of energy barrier generation hapto, thereby generates corresponding double-core product.If select suitable part and solvent for use, we can also synthesize other η by this method
6Binuclear tricarbonyl chrominium complex.For tricarbonyl chrominium complex, it compares the adding that the various beneficial properties that are enhanced all have benefited from the tricarbonyl chromium group with the aromatic ring part.And the enhancing that the increase of coordination tricarbonyl chromium group produces for the various character of complex compound is far from that simple linearity adds and.Compare with the monokaryon product, the double-core product is in the raising of aspects such as the nonlinear optical property of material and aromatic ring acidity even in index.The η of carbazole and derivative thereof
6Binuclear tricarbonyl chrominium complex will obtain using more widely aspect photoelectron, molecular designing and even the nonlinear optical material.
Description of drawings
Fig. 1 is η
6The single crystal structure figure of-vinylcarbazole tricarbonyl chromium;
Fig. 2 is double-core η
6The single crystal structure figure of-vinylcarbazole tricarbonyl chromium.
Embodiment
Below by embodiment the present invention is described in further detail: with the monokaryon η of carbazole and derivative thereof
6Tricarbonyl chrominium complex is a raw material, mixture with one or more organic coordination solvents such as dioxane, tetrahydrofuran (THF) and n-butyl ethers is a medium, employing standard Schlenk technology is carried out the deoxygenation processing, and magnetic agitation was 50 ℃ of-150 ℃ of lower seals heating 20-40 hours.After reaction finishes, adopt sherwood oil that the product system is carried out precipitate and separate.Gained double-core product is η
6Trans coordination structure, output can reach more than 30%.The tricarbonyl chrominium complex that is particularly suitable for the carbazole of this kind method and derivative thereof is as follows: η
6-carbazole tricarbonyl chromium, η
6-vinylcarbazole tricarbonyl chromium, η
6-ethyl carbazole tricarbonyl chromium, η
6-amino-ethyl carbazole tricarbonyl chromium, η
6-nitro-ethyl carbazole tricarbonyl chromium, η
6-3-aldehyde radical-9-ethyl carbazole tricarbonyl chromium, η
6-N-aminocarbazole tricarbonyl chromium, η
6-4-methoxyl group carbazole tricarbonyl chromium or η
6-4-hydroxycarbazole tricarbonyl chromium.
Preparation embodiment 1
With η
6-vinylcarbazole tricarbonyl chromium is raw material (crystalline structure is seen Fig. 1), is medium with the dioxane, prepares its saturated solution down at 25 ℃, adopts standard Schlenk technology to carry out deoxygenation and handles, and magnetic agitation was 75 ℃ of lower seals heating 30 hours.The product system adopts sherwood oil to precipitate, and vacuum drying obtains double-core η
6-vinylcarbazole tricarbonyl chromium.Products therefrom uses the mixed solvent of methylene dichloride and normal hexane to carry out crystallization at low temperatures, obtains double-core η
6The single crystal of-vinylcarbazole tricarbonyl chromium, as shown in Figure 2.
Preparation embodiment 2
According to embodiment 1 method, the employing volume ratio is that 1: 1 dioxane and n-butyl ether mixed solvent is medium, prepares its saturated solution down at 25 ℃, 120 ℃ of lower seals heating 45 hours, by η
6-ethyl carbazole tricarbonyl chromium obtains double-core η
6-ethyl carbazole tricarbonyl chromium.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. the preparation method of a binuclear tricarbonyl chrominium complex is characterized in that: with monokaryon η
6Tricarbonyl chrominium complex is a raw material, with one or more the mixture in organic coordination solvent dioxane, tetrahydrofuran (THF) or the n-butyl ether is medium, the deoxygenation of employing standard Schlenk technology, under agitation condition, 50 ℃ of-150 ℃ of heated sealed reaction 20-40h, adopt sherwood oil that reaction product is carried out precipitate and separate at last, obtain η
6The binuclear tricarbonyl chrominium complex of trans coordination structure.
2. according to the preparation method of the described a kind of binuclear tricarbonyl chrominium complex of claim 1, it is characterized in that: described monokaryon η
6The preferred η of tricarbonyl chrominium complex
6-carbazole tricarbonyl chromium, η
6-vinylcarbazole tricarbonyl chromium, η
6-ethyl carbazole tricarbonyl chromium, η
6-amino-ethyl carbazole tricarbonyl chromium, η
6-nitro-ethyl carbazole tricarbonyl chromium, η
6-3-aldehyde radical-9-ethyl carbazole tricarbonyl chromium, η
6-N-aminocarbazole tricarbonyl chromium, η
6-4-methoxyl group carbazole tricarbonyl chromium or η
6-4-hydroxycarbazole tricarbonyl chromium.
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| CNB2005100267297A CN1323084C (en) | 2005-06-14 | 2005-06-14 | Method for preparing binuclear tricarbonyl chrominium complex |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153575A (en) * | 2011-01-28 | 2011-08-17 | 阜阳师范学院 | Dioxane-coordinated rare-earth coordination compound, and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153575A (en) * | 2011-01-28 | 2011-08-17 | 阜阳师范学院 | Dioxane-coordinated rare-earth coordination compound, and preparation method and application thereof |
| CN102153575B (en) * | 2011-01-28 | 2014-07-02 | 阜阳师范学院 | Dioxane-coordinated rare-earth coordination compound, and preparation method and application thereof |
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