CN104876969A - Half-sandwich ruthenium coordination compounds, and preparation method and application thereof - Google Patents
Half-sandwich ruthenium coordination compounds, and preparation method and application thereof Download PDFInfo
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- CN104876969A CN104876969A CN201510236736.3A CN201510236736A CN104876969A CN 104876969 A CN104876969 A CN 104876969A CN 201510236736 A CN201510236736 A CN 201510236736A CN 104876969 A CN104876969 A CN 104876969A
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- PBBDILXFRBZPBH-OQLLNIDSSA-N Cc(cc1/C=N/c2ncccc2)ccc1O Chemical compound Cc(cc1/C=N/c2ncccc2)ccc1O PBBDILXFRBZPBH-OQLLNIDSSA-N 0.000 description 2
- ZUTWRNMFBRCIKF-UHFFFAOYSA-N CC(c1cc(C)ccc1O)Oc(ccc(C)c1)c1N Chemical compound CC(c1cc(C)ccc1O)Oc(ccc(C)c1)c1N ZUTWRNMFBRCIKF-UHFFFAOYSA-N 0.000 description 1
- IMJDRWOBVHDAKT-UHFFFAOYSA-N CC(c1cc(Cl)ccc1O)Oc(ccc(C)c1)c1N Chemical compound CC(c1cc(Cl)ccc1O)Oc(ccc(C)c1)c1N IMJDRWOBVHDAKT-UHFFFAOYSA-N 0.000 description 1
- FZQGBQAOJPVIOS-UHFFFAOYSA-N Cc(cc1)cc2c1[o]c(-c(cccc1)c1O)n2 Chemical compound Cc(cc1)cc2c1[o]c(-c(cccc1)c1O)n2 FZQGBQAOJPVIOS-UHFFFAOYSA-N 0.000 description 1
- 0 Cc(cc1)cc2c1[o]c(-c1cc(*)ccc1O)n2 Chemical compound Cc(cc1)cc2c1[o]c(-c1cc(*)ccc1O)n2 0.000 description 1
- RXKWERDYZGNGDB-OVCLIPMQSA-N Oc(c(/C=N/c1ncccc1)c1)ccc1Br Chemical compound Oc(c(/C=N/c1ncccc1)c1)ccc1Br RXKWERDYZGNGDB-OVCLIPMQSA-N 0.000 description 1
- DYOIUODXXXAPDU-NTEUORMPSA-N Oc1ccccc1/C=N/c1ncccc1 Chemical compound Oc1ccccc1/C=N/c1ncccc1 DYOIUODXXXAPDU-NTEUORMPSA-N 0.000 description 1
Abstract
The invention discloses half-sandwich ruthenium coordination compounds, and a preparation method and application thereof. The structure of the half-sandwich ruthenium coordination compounds is disclosed as Formula (I) or Formula (II), wherein X is halogen; m and n are respectively and independently selected from a positive integer ranging from 1 to 4; and R1 and R2 are respectively and independently selected from C1-C6 alkyl, halogen or H. The half-sandwich ruthenium coordination compounds have excellent chemical stability and solubility. The preparation method has the characteristics of simple steps and high yield.
Description
Technical field
The present invention relates to ruthenium complex, particularly, relate to a kind of half sandwich ruthenium complex and its preparation method and application.
Background technology
Organometallic complex has the feature of mineral compound and organic compound concurrently, this compounds not only makes forward position and the focus of the research field such as micro fuel cell, chiral catalysis, host-guest chemistry field, and has excellent storage odd number solution because it has adjustable spatial hole structure and large specific surface area.Wherein, ruthenium complex is outstanding person wherein.In recent years; the title complex having bibliographical information to find to have half sandwich ruthenium can improve optical property and the redox property (this is conducive to being oriented key because the structures such as phenyl ring, 1-methyl 4-isopropyl toluene and hexamethyl-benzene can shield half of metal) of ruthenium complex further; be the primary study content of the subject such as inorganic chemistry, materials chemistry, and become a field of enlivening very much in modern chemistry research gradually.Make the coordination compound with half sandwich ruthenium at photochemistry, organic catalysis, olefin metathesis, electrochemistry, fluorescent ion probe thus, the aspects such as gas sensing play important application.
Existing half sandwich ruthenium complex can be divided into covalent compound and ionic compound two kinds, and ionic compound can have excellent solubleness in polar solvent, but the solubleness of covalent compound in polar solvent is poor; In addition, the chemical stability of half sandwich ruthenium complex is also poor.Above 2 significantly limit the application limiting half sandwich ruthenium complex application in the industrial production, particularly covalent compound.
Summary of the invention
The object of this invention is to provide a kind of half sandwich ruthenium complex and its preparation method and application, this half sandwich ruthenium complex has excellent chemical stability and solvability, and the method simultaneously preparing this half sandwich ruthenium complex has the characteristic that step is simple and productive rate is high.
To achieve these goals, the invention provides a kind of half sandwich ruthenium complex, the structure of half sandwich ruthenium complex as such as formula (I) or such as formula shown in (II),
Wherein, X is halogen, m and n is selected from the positive integer in 1-4 independently of one another, R
1and R
2be selected from the alkyl of C1-C6, halogen or H independently of one another.
Present invention provides a kind of preparation method of half sandwich ruthenium complex, this preparation method comprises: under the existence of pH >=7 and rare gas element, [N, O] bidentate negative ion part and the title complex of structure as shown in formula V are carried out in organic solvent the obtained half sandwich ruthenium complex of coordination reaction; [N, O] structure of bidentate negative ion part is such as formula shown in (III) or formula (IV), such as formula the half sandwich ruthenium complex that the compound of structure (III) Suo Shi and the product after the title complex of structure carries out coordination reaction as shown in formula V are such as formula structure (I) Suo Shi, product after the title complex of structure carries out coordination reaction as shown in formula V is the half sandwich ruthenium complex such as formula structure (II) Suo Shi
Wherein, X is halogen, m and n is selected from the positive integer in 1-4 independently of one another, R
1and R
2be selected from the alkyl of C1-C6, halogen or H independently of one another.
Present invention also offers a kind of such as formula (I) or half application of sandwich ruthenium complex in organic catalysis such as formula structure (II) Suo Shi.
Pass through technique scheme, the present invention will be by carrying out the obtained half sandwich ruthenium complex such as formula structure shown in (I) or formula (II) of coordination reaction such as formula [N, O] bidentate negative ion part of structure shown in (III) or formula (IV) and the title complex of structure as shown in formula V.Compared with the title complex of structure existing formula (V) Suo Shi, although formula (I), shown in formula (II) and formula (V), the compound of structure is half sandwich ruthenium complex, but what the chlorine in the compound of structure shown in formula (V) and the phenyl ring in 1-methyl 4-isopropyl toluene and ruthenium carried out that coordination presents is the sandwich ruthenium complex of double-core half, and the nitrogen in the compound of structure shown in formula (I) and formula (II), oxygen, phenyl ring in chlorine and 1-methyl 4-isopropyl toluene and ruthenium carry out the half sandwich ruthenium complex with four coordinate bonds that half sandwich ruthenium complex that coordination makes to obtain is monokaryon, owing to using [N, O] bidentate negative ion, so the half sandwich ruthenium complex that the present invention obtains has more excellent chemical stability and solvability.In addition, preparation method provided by the invention is undertaken by single stage method, and step is simple and productive rate is high.Have on excellent chemical stability and deliquescent basis, thus facilitate this half sandwich ruthenium complex and can be able to widespread use in organic catalysis.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the X-ray single crystal diffraction figure such as formula half sandwich ruthenium complex of structure (A1) Suo Shi in embodiment 1.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of half sandwich ruthenium complex, the structure of this half sandwich ruthenium complex as such as formula (I) or such as formula shown in (II),
Wherein, X is halogen, m and n is selected from the positive integer in 1-4 independently of one another, R
1and R
2be selected from the alkyl of C1-C6, halogen or H independently of one another.The complexity obtained from raw material is considered, preferably, X is that Cl, m and n are 1, R
1and R
2be selected from the alkyl of C1-C3, halogen or H independently of one another.More preferably, X is that Cl, m and n are 1, R
1and R
2be selected from methyl, Cl, Br or H independently of one another.Further preferably, half sandwich ruthenium complex is selected from such as formula the title complex of structure (A1)-Shi (A4) Suo Shi and the title complex such as formula structure (B1)-Shi (B4) Suo Shi,
Present invention provides a kind of preparation method of half sandwich ruthenium complex, this preparation method comprises: under the existence of pH >=7 and rare gas element, [N, O] bidentate negative ion part and the title complex of structure as shown in formula V are carried out in organic solvent the obtained half sandwich ruthenium complex of coordination reaction; [N, O] structure of bidentate negative ion part is such as formula shown in (III) or formula (IV), such as formula the half sandwich ruthenium complex that the compound of structure (III) Suo Shi and the product after the title complex of structure carries out coordination reaction as shown in formula V are such as formula structure (I) Suo Shi, product after the title complex of structure carries out coordination reaction as shown in formula V is the half sandwich ruthenium complex such as formula structure (II) Suo Shi
Wherein, X is halogen, m and n is selected from the positive integer in 1-4 independently of one another, R
1and R
2be selected from the alkyl of C1-C6, halogen or H independently of one another.The complexity obtained from raw material is considered, preferably, X is that Cl, m and n are 1, R
1and R
2be selected from the alkyl of C1-C3, halogen or H independently of one another.More preferably, X is that Cl, m and n are 1, R
1and R
2be selected from methyl, Cl, Br or H independently of one another.Further preferably, compound such as formula structure (III) Suo Shi is selected from the compound such as formula structure (C1)-Shi (C4) Suo Shi, compound such as formula structure (IV) Suo Shi is selected from the compound such as formula structure (D1)-Shi (D4) Suo Shi
In preparation method provided by the invention, the concrete consumption of each raw material can be selected in wide scope, but in order to make the method, there is more excellent productive rate, preferably, relative to the title complex of 1mmol structure as shown in formula V, the consumption of [N, O] bidentate negative ion part is 2-3mmol, and the consumption of organic solvent is 1-5mmol.
Meanwhile, the temperature and time of this coordination reaction can be selected in wide scope, but in order to make this coordination reaction have more excellent productive rate and speed, preferably, coordination reaction meets following condition: temperature of reaction is 65-90 DEG C, and the reaction times is 5-10h.
In invention, the concrete kind of rare gas element can be selected equally in wide scope, as long as ensure that this coordination reaction occurs just can in the atmosphere of inertia, but taking cost into account, preferably, rare gas element be selected from argon gas, nitrogen and helium one or more, be preferably nitrogen.
The pH of above-mentioned coordination reaction system can select, as long as OH in wide scope
-1can in time in and by product HCl thus promote coordination reaction carry out towards the direction of positive reaction just can, but consider the productive rate of reaction, preferably, the pH of described coordination reaction is 7-11.
In addition, regulate the mode of the pH of this coordination reaction can be any one mode in this area, as long as make the system of this coordination reaction can in time in and in coordination reaction the by product HCl that generates just can, and then promote the carrying out of this coordination reaction, preferably, the pH of coordination reaction is regulated by one or more in carbonate, supercarbonate, mineral alkali (as sodium hydroxide) and organic bases (as triethylamine), regulates preferably by salt of wormwood.
On the basis of the above, the effect of the just solubilizing reaction thing that organic solvent plays, concrete kind can be selected in wide scope, but consider from solvability, preferably, organic solvent be selected from methyl alcohol, ethanol and acetonitrile one or more, be preferably methyl alcohol.
Present invention also offers a kind of such as formula (I) or half application of sandwich ruthenium complex in organic catalysis such as formula structure (II) Suo Shi.
Below will be described the present invention by embodiment.In following examples, nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum parameter are recorded by Switzerland Bruker AV300 and Bruker AV 500MHz nuclear magnetic resonance analyser, and X-ray single crystal diffraction parameter is recorded by Bruker AXS single crystal diffractometer SMART APEX II.
The title complex of structure i.e. (CymeneRuCl as shown in formula V
2)
2for the product of Shanghai company of Jing Chun biochemical technology limited-liability company, salt of wormwood is the product of Shanghai company of Jing Chun biochemical technology limited-liability company, methyl alcohol is the product of Shanghai company of Jing Chun biochemical technology limited-liability company, such as formula the compound of structure (C1)-Shi (C4) Suo Shi all according to document " X.C.Shi, G.-X.Jin, Organometallics 2012, 31, 7198-7205. " method reported is prepared from, such as formula the compound of structure (D1)-Shi (D4) Suo Shi all according to document " M.Enamullah, M.A.Quddus, M.A.Halim, M.K.Islam, V.Vasylyeva, C.Janiak, Inorganica Chimica Acta, 427 (2015) 103-111. " method reported is prepared from.
Embodiment 1
At the protection of nitrogen and 75 DEG C, by [CymeneRu (μ-Cl) Cl] of 306mg (0.5mmol)
2, the compound such as formula structure (C1) Suo Shi of 287mg (1.2mmol), the salt of wormwood (pH of reaction system is adjusted to 8) of 193mg (1.4mmol) and 50mL methyl alcohol (purity is 99%) mixing, backflow 5h, be cooled to 25 DEG C, underpressure distillation is except desolventizing, obtain safran powder 346mg with drying after the methanol wash of 5 DEG C, productive rate is 68%.
The characterization data of this safran powder is:
1h NMR (300MHz, CDCl
3, ppm): δ 7.51 (d, 2H), 7.42 (s, 1H), 7.17 (d, 1H), 7.07 (d, 2H), 5.54 (d, 1H), 5.47 (s, 1H), 5.42 (d, 1H), 5.35 (d, 1H), 2.77 (m 1H), 2.52 (s 3H), 2.25 (s 6H), 1.19 (d 3H), 1.10 (d, 3H);
13c NMR (500MHz, CDCl
3, ppm): 168.23,160.64,148.24,141.34,135.70,135.33,126.85,126.25,123.89,123.81,118.86,110.37,110.26,102.63,97.54,83.54,81.95,80.10,79.78,30.78,22.71,21.84,21.77,20.31,18.90.IR (KBrcm-1): 3052 (w), 2969 (w), 2912 (w), 2861 (w), 1626 (m), 1556 (s), 1485 (m), 1339 (m), 1250 (w), 830 (w); X-ray single crystal diffraction figure is shown in Fig. 1.As can be seen here, the structure of this safran powder is such as formula shown in (A1).
Embodiment 2
Obtained 402mg safran powder (productive rate is 76%) is carried out according to the method for embodiment 1, difference is the compound such as formula structure (C2) Suo Shi the compound such as formula structure (C1) Suo Shi of 1.2mmol being changed into 311mg (1.2mmol), and the reaction times is changed to 8h.
The characterization data of this safran powder is:
1h NMR (300MHz, CDCl
3, ppm): δ 7.70 (d, 1H), 7.47 (t, 2H), 7.21 (t, 2H), 7.03 (d, 1H), 5.54 (m, 4H), 2.77 (s 1H), 2.53 (s3H), 2.28 (s 3H), 1.20 (d 3H), 1.11 (d, 3H)
13c NMR (500MHz, CDCl
3, ppm): 168.51,159.49,148.19,141.17,135.70,134.08,126.86,126.45,125.64,119.11,118.94,111.46,110.52,102.89,97.85,83.74,82.04,80.19,79.59,30.84,22.67,21.85,21.81,18.93.IR (KBr cm
-1): 3041 (w), 2971 (w), 2915 (w), 2869 (w), 1600 (m), 1551 (m), 1518 (m), 1458 (s), 1396 (m), 1334 (m), 1235 (m), 1186 (m), 1098 (w), 1052 (w), 819 (m), 724 (m), 658 (w), 592 (w), 533 (w).As can be seen here, the structure of this safran powder is such as formula shown in (A2).
Embodiment 3
Obtained 458mg safran powder (productive rate is 80%) is carried out according to the method for embodiment 1, difference is the compound such as formula structure (C3) Suo Shi the compound such as formula structure (C1) Suo Shi of 1.2mmol being changed into 363mg (1.2mmol), and the reaction times is changed to 10h.
The characterization data of this safran powder is:
1h NMR (500MHz, CDCl
3, ppm): δ 7.84 (d, 1H), 7.47 (s, 1H), 7.43 (d, 1H), 7.26 (m, 1H), 7.19 (d, 1H), 6.97 (d, 1H), 5.55 (d, 1H), 5.49 (d, 1H), 5.43 (d, 1H), 5.35 (d, 1H), 2.75 (s 1H), 2.52 (s 3H), 2.27 (s 3H), 1.20 (d 3H), 1.11 (d, 3H)
13c NMR (500MHz, CDCl
3, ppm): 168.85,159.32,148.15,141.12,136.65,135.69,129.50,126.86,126.08,118.91,112.28,110.51,105.74,102.86,97.82,83.72,81.99,80.21,79.55,77.70,77.44,77.19,30.82,22.67,21.85,21.80,18.93.IR (KBr cm
-1): 3070 (w), 3041 (w), 2968 (w), 2959 (w), 2919 (w), 2866 (w), 1597 (m), 1511 (m), 1521 (m), 1462 (s), 1393 (m), 1311 (m), 1256 (m), 1232 (m), 1186 (m), 1085 (w), 947 (w), 895 (w), 872 (w), 849 (w), 816 (m), 708 (m), 648 (m), 589 (w), 530 (w).As can be seen here, the structure of this safran powder is such as formula shown in (A3).
Embodiment 4
Obtained 432mg safran powder (productive rate is 85%) is carried out according to the method for embodiment 1, difference is the compound such as formula structure (C4) Suo Shi the compound such as formula structure (C1) Suo Shi of 1.2mmol being changed into 270mg (1.2mmol), and the reaction times is changed to 10h.
The characterization data of this safran powder is:
1h NMR (500MHz, CDCl
3, ppm): δ 7.84 (d, 1H), 7.47 (s, 1H), 7.44 (d, 1H), 7.27 (m, 1H), 7.20 (d, 1H), 6.98 (d, 1H), 5.55 (d, 1H), 5.49 (d, 1H), 5.43 (d, 1H), 5.35 (d, 1H), 2.75 (s 1H), 2.26 (s 3H), 1.21 (d 3H), 1.12 (d, 3H)
13c NMR (500MHz, CDCl
3, ppm): 166.45,158.35,147.20,141.12,135.55,135.69,129.40,126.66,125.08,117.91,111.28,112.44,103.74,102.86,96.52,82.77,80.99,79.81,79.55,77.70,76.44,77.19,22.80,21.66,21.45,19.93.IR (KBr cm
-1): 3071 (w), 3042 (w), 2966 (w), 2958 (w), 2919 (w), 2876 (w), 1598 (m), 1521 (m), 1511 (m), 1462 (s), 1390 (m), 1311 (m), 1255 (m), 1230 (m), 1185 (m), 1085 (w), 946 (w), 896 (w), 870 (w), 849 (w), 815 (m), 710 (m).As can be seen here, the structure of this safran powder is such as formula shown in (A4).
Embodiment 5
Obtained 330mg safran powder (productive rate is 63%) is carried out according to the method for embodiment 1, difference is the compound such as formula structure (D1) Suo Shi the compound such as formula structure (C1) Suo Shi of 1.2mmol being changed into 255mg (1.2mmol), and the reaction times is changed to 7h.
The characterization data of this safran powder is:
1h NMR (300MHz, CDCl
3, ppm) and δ 8.50 (d, J=3.9Hz, 1H), 8.14 (d, J=8.1Hz, 1H), 7.97 (s, 1H), 7.79 (t, 1H), 7.30 (t, 1H), 7.07 (d, J=8.4Hz, 1H), 6.95 (d, J=8.7Hz, 1H), 6.79 (s, 1H), 5.37 (d, J=6.0Hz, 1H), 5.26 (d, J=6.0Hz, 1H), 5.15 (d, J=5.7Hz, 1H), 4.43 (d, J=5.7Hz, 1H), 2.63 (m, 1H), 2.13 (s, 3H), 2.08 (s, 3H), 1.12 (m, 6H)
13c NMR (300MHz, CDCl
3, ppm) and δ 164.47,164.29,147.70,137.95,137.74,134.77,123.10,122.78,122.44,121.39,117.84,101.76,97.98,85.29,82.84,82.43,80.63,30.38,22.43,21.95,19.92,18.46.IR (KBr cm
-1): 3012,2920,2838,1619,1584,1455,1433,1279,1151,892,834,740,600,529.As can be seen here, the structure of this safran powder is such as formula shown in (B1).
Embodiment 6
Carry out obtained 409mg safran powder (productive rate is 75%) according to the method for embodiment 5, difference is the compound such as formula structure (D2) Suo Shi the compound such as formula structure (D1) Suo Shi of 1.2mmol being changed into 283mg (1.2mmol).
The characterization data of this safran powder is:
1h NMR (300MHz, CDCl
3, ppm) and δ 8.49 (d, J=3.9Hz, 1H), 8.10 (d, J=8.1Hz, 1H), 7.94 (s, 1H), 7.80 (t, 1H), 7.32 (t, 2H), 7.14 (t, 1H), 6.98 (m, 2H), 5.38 (d, J=5.7Hz, 1H), 5.25 (d, J=5.7Hz, 1H), 5.15 (d, J=5.4Hz, 1H), 4.43 (d, J=5.7Hz, 1H), 2.62 (t, 1H), 2.08 (s, 3H), 1.12 (m, 6H)
13c NMR (300MHz, CDCl
3, ppm) and δ 166.67,164.63,163.82,147.81,138.11,135.78,133.71,124.68,122.82,121.12,118.84,118.37,102.11,98.20,85.37,83.06,82.33,80.83,30.41,22.40,21.93,18.47.IR (KBr cm
-1): 3077,3041,2932,2850,1628,1583,1555,1491,1428,1273,1181,1145,990,872,740,644,580,525.As can be seen here, the structure of this safran powder is such as formula shown in (B2).
Embodiment 7
Carry out obtained 390mg safran powder (productive rate is 67%) according to the method for embodiment 5, difference is the compound such as formula structure (D3) Suo Shi the compound such as formula structure (D1) Suo Shi of 1.2mmol being changed into 332mg (1.2mmol).
The characterization data of this safran powder is:
1h NMR (300MHz, CDCl
3, ppm) and δ 8.48 (s, 1H), 8.08 (d, J=7.8Hz, 1H), 7.94 (s, 1H), 7.80 (m, 1H), 7.32 (m, 2H), 7.12 (s, 1H), 6.91 (d, J=9.0Hz, 1H), 5.38 (d, J=5.4Hz, 1H), 5.26 (d, J=5.7Hz, 1H), 5.15 (d, J=5.1Hz, 1H), 4.43 (d, J=5.4Hz, 1H), 2.62 (s, 1H), 2.07 (s, 3H), 1.12 (m, 6H)
13c NMR (500MHz, CDCl
3, ppm) and δ 167.06,165.34,164.19,148.21,138.73,138.51,137.31,125.48,123.22,121.49,120.18,105.45,102.57,98.62,85.75,83.47,82.73,81.27,30.81,22.78,22.33,18.85.IR (KBr cm
-1): 3050,2932,2850,1610,1580,1555,1373,1273,1181,990,817,790,735,635.As can be seen here, the structure of this safran powder is such as formula shown in (B3).
Embodiment 8
Carry out obtained 400mg safran powder (productive rate is 80%) according to the method for embodiment 5, difference is the compound such as formula structure (D4) Suo Shi the compound such as formula structure (D1) Suo Shi of 1.2mmol being changed into 237mg (1.2mmol).
The characterization data of this safran powder is:
1h NMR (300MHz, CDCl
3, ppm) and δ 8.48 (d, J=3.9Hz, 1H), 8.12 (d, J=8.1Hz, 1H), 8.02 (s, 1H), 7.77 (m, 1H), 7.29 (m, 2H), 7.00 (d, J=8.1Hz, 2H), 6.43 (m, 1H), 5.36 (d, J=5.7Hz, 1H), 5.26 (d, J=5.1Hz, 1H), 5.14 (d, J=5.4Hz, 1H), 4.44 (d, J=5.4Hz, 1H), 2.61 (m, 1H), 2.06 (s, 3H), 1.10 (m, 6H)
13c NMR (300MHz, CDCl
3, ppm) and δ 166.89,165.97,164.67,147.73,138.02,135.91,135.88,123.04,122.600,121.32,118.40,114.49,101.90,98.00,85.2682.95,82.40,80.67,30.38,22.42,21.89,18.46.IR (KBr cm
-1): 3059,2922,2840,1610,1580,1550,1464,1428,1281,1181,1145,999,835,790,762,580,535.As can be seen here, the structure of this safran powder is such as formula shown in (B4).
Embodiment 9
Carry out obtained 314mg safran powder (productive rate is 60%) according to the method for embodiment 1, difference changes the consumption of the compound such as formula structure (C1) Suo Shi into 239mg (1mmol).
The characterization data of this safran powder is identical with embodiment 1, and as can be seen here, the structure of this safran powder is such as formula shown in (A1).
Embodiment 10
Carry out obtained 419mg safran powder (productive rate is 80%) according to the method for embodiment 1, difference changes the consumption of the compound such as formula structure (C1) Suo Shi into 359mg (1.5mmol).
The characterization data of this safran powder is identical with embodiment 1, and as can be seen here, the structure of this safran powder is such as formula shown in (A1).
Embodiment 11
Carry out obtained 325mg safran powder (productive rate is 62%) according to the method for embodiment 1, difference the consumption of salt of wormwood is changed into 137mg (1mmol) to make the pH of reaction system be 7.2.
The characterization data of this safran powder is identical with embodiment 1, and as can be seen here, the structure of this safran powder is such as formula shown in (A1).
Embodiment 12
Carry out obtained 393mg safran powder (productive rate is 75%) according to the method for embodiment 1, difference the consumption of salt of wormwood is changed into 415mg (3mmol) to make the pH of reaction system be 10.
The characterization data of this safran powder is identical with embodiment 1, and as can be seen here, the structure of this safran powder is such as formula shown in (A1).
Embodiment 12
Carry out according to the method for embodiment 1, difference is the pH of reaction system is 11, and result is obtained 367mg safran powder (productive rate is 70%).
Comparative example 1
Carry out according to the method for embodiment 1, difference is inert-free gas protection, and result is obtained 183mg safran powder (productive rate is 35%)
Comparative example 2
Carry out according to the method for embodiment 1, difference is the pH of reaction system is 6, and result is obtained 27mg safran powder (productive rate is 5%)
Test example 1
Will such as formula (A1)-Shi (A4), formula (B1)-Shi (B4) and CymeneRuCl
2shown in structure half sandwich ruthenium complex respectively uncovered be placed in 20 DEG C at 48h, then detect the purity W of each title complex, the results are shown in Table 1.
Test example 2
At 20 DEG C, will such as formula (A1)-Shi (A4), formula (B1)-Shi (B4) and CymeneRuCl
2half sandwich ruthenium complex of shown structure is dissolved in methyl alcohol respectively, calculates the solubleness s of each title complex, the results are shown in Table 1.
Table 1
| V | A1 | A2 | A3 | A4 | B1 | B2 | B3 | B4 | |
| w(％) | 99 | 99.5 | 99.6 | 99.8 | 99.9 | 100 | 100 | 99.9 | 99.8 |
| S (g/100g methyl alcohol) | 1.26 | 2.91 | 3.03 | 2.98 | 2.93 | 2.28 | 2.39 | 2.25 | 2.33 |
V in upper table refers to (CymeneRuCl
2)
2, A1-A4 is obtained is respectively half sandwich ruthenium complex such as formula structure (A1)-Shi (A4) Suo Shi, and it is half sandwich ruthenium complex such as formula structure (B1)-Shi (B4) Suo Shi that B1-B4 obtains respectively.
From above-described embodiment, comparative example and test example, preparation method provided by the invention can obtain the half sandwich ruthenium complex such as formula structure (A1)-Shi (A4) and formula (B1)-Shi (B4) Suo Shi, and this half sandwich ruthenium complex has excellent chemical stability and solvability simultaneously.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a half sandwich ruthenium complex, is characterized in that, the structure of described half sandwich ruthenium complex as such as formula (I) or such as formula shown in (II),
Wherein, X is halogen, m and n is selected from the positive integer in 1-4 independently of one another, R
1and R
2be selected from the alkyl of C1-C6, halogen or H independently of one another.
2. half sandwich ruthenium complex according to claim 1, wherein, X is that Cl, m and n are 1, R
1and R
2be selected from the alkyl of C1-C3, halogen or H independently of one another;
Preferably, X is that Cl, m and n are 1, R
1and R
2be selected from methyl, Cl, Br or H independently of one another;
More preferably, described half sandwich ruthenium complex is selected from such as formula the title complex of structure (A1)-Shi (A4) Suo Shi and the title complex such as formula structure (B1)-Shi (B4) Suo Shi,
3. the preparation method of one and half sandwich ruthenium complexes, it is characterized in that, described preparation method comprises: under the existence of pH >=7 and rare gas element, [N, O] bidentate negative ion part and the title complex of structure as shown in formula V are carried out in organic solvent the obtained half sandwich ruthenium complex of coordination reaction; Described [N, O] structure of bidentate negative ion part is such as formula shown in (III) or formula (IV), such as formula the half sandwich ruthenium complex that the compound of structure (III) Suo Shi and the product after the title complex of structure carries out coordination reaction as shown in formula V are such as formula structure (I) Suo Shi, product after the title complex of structure carries out coordination reaction as shown in formula V is the half sandwich ruthenium complex such as formula structure (II) Suo Shi
Wherein, X is halogen, m and n is selected from the positive integer in 1-4 independently of one another, R
1and R
2be selected from the alkyl of C1-C6, halogen or H independently of one another.
4. preparation method according to claim 3, wherein, X is that Cl, m and n are 1, R
1and R
2be selected from the alkyl of C1-C3, halogen or H independently of one another;
Preferably, X is that Cl, m and n are 1, R
1and R
2be selected from methyl, Cl, Br or H independently of one another;
More preferably, the described compound such as formula structure (III) Suo Shi is selected from the compound such as formula structure (C1)-Shi (C4) Suo Shi, the described compound such as formula structure (IV) Suo Shi is selected from the compound such as formula structure (D1)-Shi (D4) Suo Shi
5. the preparation method according to claim 3 or 4, wherein, relative to described in 1mmol as shown in formula V the title complex of structure, the consumption of described [N, O] bidentate negative ion part is 2-3mmol, and the consumption of described organic solvent is 1-5mmol.
6. the preparation method according to claim 3 or 4, wherein, described coordination reaction meets following condition: temperature of reaction is 65-90 DEG C, and the reaction times is 5-10h.
7. the preparation method according to claim 3 or 4, wherein, described rare gas element be selected from argon gas, nitrogen and helium one or more, be preferably nitrogen.
8. the preparation method according to claim 3 or 4, wherein, the pH of described coordination reaction is 7-11;
Preferably, the pH of described coordination reaction is regulated by one or more in carbonate, supercarbonate, mineral alkali and organic bases, regulates preferably by salt of wormwood.
9. the preparation method according to claim 3 or 4, wherein, described organic solvent be selected from methyl alcohol, ethanol and acetonitrile one or more, be preferably methyl alcohol.
10. one kind such as formula (I) or half application of sandwich ruthenium complex in catalyse organic reaction such as formula structure (II) Suo Shi.
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| CN106349295A (en) * | 2016-08-24 | 2017-01-25 | 安徽师范大学 | Hydroxyl-containing half-sandwich rutheniumcoordination compound, preparation method and method for reducing nitrobenzene compound into aniline compound |
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| CN110938086B (en) * | 2019-11-20 | 2023-04-18 | 安徽师范大学 | Half-sandwich ruthenium-thione complex and preparation method thereof, ammonia borane hydrolysis method and nitrobenzene compound reduction method |
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