CN103739628B - A kind of containing multiple carborane group three core ruthenium duster compound crystal and preparation method thereof - Google Patents
A kind of containing multiple carborane group three core ruthenium duster compound crystal and preparation method thereof Download PDFInfo
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- CN103739628B CN103739628B CN201310415992.XA CN201310415992A CN103739628B CN 103739628 B CN103739628 B CN 103739628B CN 201310415992 A CN201310415992 A CN 201310415992A CN 103739628 B CN103739628 B CN 103739628B
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- ruthenium
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Abstract
The present invention relates to a kind of containing multiple carborane group three core ruthenium duster compound crystal and preparation method thereof, belong to organometallic chemistry technical field.The structure of this duster compound through Advances in crystal X-ray diffraction and nucleus magnetic resonance (
1h? etc. NMR) method characterizes and is confirmed, crystal belongs to oblique system, spacer P2
1/ c, molecular formula is C
32h
66b
30oRu
3se
6cH
2cl
2h
2o, molecular weight is 1671.06.The present invention uses 1,2-bis-carbon generation-enclosed-ten two carborane, n-Butyl Lithium, selenium powder and dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimer are starting raw material, after stirring reaction, directly add the method for methylene dichloride and 1-ethynylcyclohexanol after taking to drain solvent, " one kettle way " is obtained containing multiple carborane group three core ruthenium duster compound.Duster compound crystal of the present invention has good chemical stability and solvability, and preparation method is simple, is with a wide range of applications.
Description
Technical field
The invention belongs to organometallic chemistry technical field, be specifically related to a kind of containing multiple carborane group three core ruthenium duster compound crystal and preparation method thereof.
Background technology
Due to molecular structure and the application potential in synthetic materials, microelectronics, optics and medicine etc. of 1,2-bis-carbon generation-enclosed-ten two carborane derivative uniqueness, the research about this kind of carborane derivative causes people's interest widely.Research show containing sulfur family elemental carbon borine organometallic compound can controllability generation number of chemical reaction: by inserting alkynes carbon carbon triple bond thus cause B-H bond activation in metal-sulfur race element singly-bound, realize the functionalization of B (3)/B (6) position at ortho position-carborane; Easily with lower valency transistion metal compound generation redox reaction, sulphur (selenium) element connects different metals as abutment, formed contain Metal-Metal bond double-core or polynuclear compounds.(as: LiuS, HanYF, JinGX.Chem.Soc.Rev., 2007,36,1543; YaoZJ, JinGX.Organometallics, 2011,30,5365; ZhangJS, LinYJ, JinGX.J.Organomet.Chem., 2009,694,2069; LiYG, JiangQB, ZhangXL, LiYZ, YanH, BregadzeVI.Inorg.Chem., 2010,49,3911; HuJR, LiuGF, JiangQB, ZhangR, HuangW, YanH.Inorg.Chem., 2010,49,11199).
Based on containing the uncertainty of sulfur family element ligand transient metal complex compound synthesis mode and the rich of the coordination chemistry of sulfur family element own, containing sulfur family elemental carbon borine part because the structure that its system contains carborane uniqueness makes it have the incomparable feature of other parts, the research about this kind of organometallic compound has become a very active field of modern chemistry research.(as: WangJQ, CaiSY, JinGX, WengLH, HerberholdM.Chem.Eur.J., 2005,11,7342; MengX, WangFS, JinGX.Coord.Chem.Rev., 2010,254,1260; JinGX.Coord.Chem.Rev., 2004,248,587; MoriS, MochidaT.Organometallics, 2013,32,780).The invention discloses a kind of containing multiple carborane group three core ruthenium duster compound crystal and preparation method thereof, have found one facilitate approach for design and synthesis contains Ru-Ru key metal cluster compound.
Summary of the invention
The object of the invention is to open one containing multiple carborane group three core ruthenium duster compound crystal and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is as follows:
Duster compound crystal of the present invention is the duster compound crystal of following chemical formula: (p-cymene) Ru
3(Se
2c
2b
10h
10)
2(Se
2c
2b
10h
9) [HC-CH (cyclo-C
6h
10) OC-CH (cyclo-C
6h
10)] CH
2cl
2h
2o, wherein p-cymene=p-Methylisopropylbenzene base, cyclo-C
6h
10=cyclohexyl; Its skeleton symbol is as follows:
Described duster compound crystal belongs to oblique system, spacer P2
1/ c, molecular formula C
32h
66b
30oRu
3se
6cH
2cl
2h
2o, molecular weight=1671.06, unit cell parameters:
a=90 °, β=99.977 (3) °, γ=90 °,
z=4, R
1=0.0413, wR
2=0.0983.
The basic structure of described duster compound is the Ru atom being in central position is seven coordinations, and ligating atom is two (Se
2c
2b
10h
10)
2-group provides three Se atoms, (a Se
2c
2b
10h
9)
3-group provides two Se atoms and two Ru atoms from Metal-Metal bond, and these seven ligating atoms are being in the pentagonal bipyramid geometric configuration defining a distortion around the Ru atom of central position; Be in an extraneous metal Ru atom and still remain 6e neutral ligand p-Methylisopropylbenzene base, and the p-Methylisopropylbenzene base be connected with another metal Ru atom disappears due to the coordination of 1-ethynylcyclohexanol; With regard to bond distance, the distance of Ru-Ru metallic bond is respectively
belong to the bond distance of typical Ru-Ru singly-bound.
Under argon shield, by 1,2-bis-carbon generation-enclosed-ten two carborane is dissolved in anhydrous diethyl ether, add n-Butyl Lithium, selenium powder successively, after stirring and dissolving, to be dissolved with dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimeric tetrahydrofuran solution adds in above-mentioned reaction flask, temperature control 0 DEG C, and stirring reaction 4 hours final vacuums drain solvent; Use methylene dichloride lysate, add 1-ethynylcyclohexanol, temperature control 20-25 DEG C, stirring reaction 23-24 hour, reaction solution is concentrated into dry; Sherwood oil (60-90 DEG C) is eluent with the mixed solution of methylene dichloride, crosses the separation of 200-300 order silicagel column and obtains target duster compound; Carry out crystallization with sherwood oil (60-90 DEG C) and the mixed solvent of methylene dichloride, obtain yellow bulk crystals.
The volume ratio of organic solvent anhydrous diethyl ether, tetrahydrofuran (THF) and methylene dichloride that described reaction system uses is 1: 2: 1.
The mol ratio of described 1,2-bis-carbon generation-enclosed-ten two carborane, n-Butyl Lithium, selenium powder, dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimer and 1-ethynylcyclohexanol is 3: 6: 9: 2: 2.
Described eluent by sherwood oil (60-90 DEG C) and methylene dichloride by 2: 1 volume ratio mixture form.
The mixed solvent that described crystallization uses by sherwood oil (60-90 DEG C) and methylene dichloride by 1: 1 volume ratio mixture form.
Accompanying drawing explanation
Fig. 1 is duster compound crystal (p-cymene) Ru of the present invention
3(Se
2c
2b
10h
10)
2(Se
2c
2b
10h
9) [HC-CH (cyclo-C
6h
10) OC-CH (cyclo-C
6h
10)] CH
2cl
2h
2o (wherein p-cymene=p-Methylisopropylbenzene base, cyclo-C
6h
10=cyclohexyl) molecular structure ellipsoid figure.
Embodiment
Duster compound crystal of the present invention belongs to oblique system, spacer P2
1/ c, molecular formula C
32h
66b
30oRu
3se
6cH
2cl
2h
2o, molecular weight=1671.06, unit cell parameters:
α=90 °, β=99.977 (3) °, γ=90 °,
z=4, R
1=0.0413, wR
2=0.0983.Its basic structure is the Ru atom being in central position is seven coordinations, and ligating atom is two (Se
2c
2b
10h
10)
2-group provides three Se atoms, (a Se
2c
2b
10h
9)
3-group provides two Se atoms and two Ru atoms from Metal-Metal bond, and these seven ligating atoms are being in the pentagonal bipyramid geometric configuration defining a distortion around the Ru atom of central position; Be in an extraneous metal Ru atom and still remain 6e neutral ligand p-Methylisopropylbenzene base, and the p-Methylisopropylbenzene base be connected with another metal Ru atom disappears due to the coordination of 1-ethynylcyclohexanol; With regard to bond distance, the distance of Ru-Ru metallic bond is respectively
belong to the bond distance of typical Ru-Ru singly-bound.
In the preparation method of duster compound crystal of the present invention, under argon shield, by 1,2-bis-carbon generation-enclosed-ten two carborane is dissolved in anhydrous diethyl ether, add n-Butyl Lithium, selenium powder successively, after stirring and dissolving, dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimeric tetrahydrofuran solution will be dissolved with and add in above-mentioned reaction flask, temperature control 0 DEG C, stirring reaction 4 hours final vacuums drain solvent; Use methylene dichloride lysate, add 1-ethynylcyclohexanol, temperature control 20-25 DEG C, stirring reaction 23-24 hour, reaction solution is concentrated into dry; Sherwood oil (60-90 DEG C) is eluent with the mixed solution of methylene dichloride, crosses the separation of 200-300 order silicagel column and obtains target duster compound; Carry out crystallization with sherwood oil (60-90 DEG C) and the mixed solvent of methylene dichloride, obtain yellow bulk crystals.
Embodiment 1
Under argon shield, 1,2-bis-carbon generation-enclosed-ten two carborane (86mg, 0.6mmol) is dissolved in 20mL anhydrous diethyl ether, adds n-Butyl Lithium (2.0molL successively
-1cyclohexane solution) (0.6mL, 1.2mmol), selenium powder (142mg, 1.8mmol), after stirring and dissolving, add and be dissolved with dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimer (245mg, tetrahydrofuran solution 40mL 0.4mmol), temperature control 0 DEG C, reacts and drains solvent through vacuum after 4 hours; With 20mL methylene dichloride lysate, added by 1-ethynylcyclohexanol (50mg, 0.4mmol) in above-mentioned reaction flask, reaction solution, after 23 hours, is concentrated into dry by temperature control 20 DEG C reaction; Cross the separation of 200-300 order silicagel column and obtain target duster compound (72mg, 23%) (eluent: V (sherwood oil (60-90 DEG C))/V (methylene dichloride)=2: 1); This duster compound is dissolved in the mixed solvent of sherwood oil (60-90 DEG C) and methylene dichloride and carries out crystallization (V (sherwood oil (60-90 DEG C))/V (methylene dichloride)=1: 1), obtain yellow bulk crystals.Fusing point: 238 DEG C;
1hNMR (CDCl
3): δ 1.24,1.36 (d, J=7.0Hz, 3H, CH (CH
3)
2), 1.47,1.75,1.92,2.08,2.32 (m, 2H, CH
2, cyclo-C
6h
10), 2.50 (s, 3H, C
6h
4-CH
3), 3.02 (sept.J=7.0Hz, 1H, CH (CH
3)
2), 3.34 (d, J=12.0Hz, 1H, B-CH-CH), 4.52 (d, J=12.0Hz, 1H, B-CH-CH), 5.63,5.81,5,97,5.99 (d, J=6.0Hz, 1H, C
6h
4), 6.37 (s, 1H, C=CH).
Embodiment 2
Under argon shield, 1,2-bis-carbon generation-enclosed-ten two carborane (86mg, 0.6mmol) is dissolved in 20mL anhydrous diethyl ether, adds n-Butyl Lithium (2.0molL successively
-1cyclohexane solution) (0.6mL, 1.2mmol), selenium powder (142mg, 1.8mmol), after stirring and dissolving, add and be dissolved with dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimer (245mg, tetrahydrofuran solution 40mL 0.4mmol), temperature control 0 DEG C, reacts and drains solvent through vacuum after 4 hours; With 20mL methylene dichloride lysate, added by 1-ethynylcyclohexanol (50mg, 0.4mmol) in above-mentioned reaction flask, reaction solution, after 24 hours, is concentrated into dry by temperature control 20 DEG C reaction; Cross the separation of 200-300 order silicagel column and obtain target duster compound (78mg, 25%) (eluent: V (sherwood oil (60-90 DEG C))/V (methylene dichloride)=2: 1); This duster compound is dissolved in the mixed solvent of sherwood oil (60-90 DEG C) and methylene dichloride and carries out crystallization (V (sherwood oil (60-90 DEG C))/V (methylene dichloride)=1: 1), obtain yellow bulk crystals.Fusing point: 238 DEG C;
1hNMR (CDCl
3): δ 1.24,1.36 (d, J=7.0Hz, 3H, CH (CH
3)
2), 1.47,1.75,1.92,2.08,2.32 (m, 2H, CH
2, cyclo-C
6h
10), 2.50 (s, 3H, C
6h
4-CH
3), 3.02 (sept.J=7.0Hz, 1H, CH (CH
3)
2), 3.34 (d, J=12.0Hz, 1H, B-CH-CH), 4.52 (d, J=12.0Hz, 1H, B-CH-CH), 5.63,5.81,5,97,5.99 (d, J=6.0Hz, 1H, C
6h
4), 6.37 (s, 1H, C=CH).
Embodiment 3
Under argon shield, 1,2-bis-carbon generation-enclosed-ten two carborane (86mg, 0.6mmol) is dissolved in 20mL anhydrous diethyl ether, adds n-Butyl Lithium (2.0molL successively
-1cyclohexane solution) (0.6mL, 1.2mmol), selenium powder (142mg, 1.8mmol), after stirring and dissolving, add and be dissolved with dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimer (245mg, tetrahydrofuran solution 40mL 0.4mmol), temperature control 0 DEG C, reacts and drains solvent through vacuum after 4 hours; With 20mL methylene dichloride lysate, added by 1-ethynylcyclohexanol (50mg, 0.4mmol) in above-mentioned reaction flask, reaction solution, after 23 hours, is concentrated into dry by temperature control 25 DEG C reaction; Cross the separation of 200-300 order silicagel column and obtain target duster compound (75mg, 24%) (eluent: V (sherwood oil (60-90 DEG C))/V (methylene dichloride)=2: 1); This duster compound is dissolved in the mixed solvent of sherwood oil (60-90 DEG C) and methylene dichloride and carries out crystallization (V (sherwood oil (60-90 DEG C))/V (methylene dichloride)=1: 1), obtain yellow bulk crystals.Fusing point: 238 DEG C;
1hNMR (CDCl
3): δ 1.24,1.36 (d, J=7.0Hz, 3H, CH (CH
3)
2), 1.47,1.75,1.92,2.08,2.32 (m, 2H, CH
2, cyclo-C
6h
10), 2.50 (s, 3H, C
6h
4-CH
3), 3.02 (sept.J=7.0Hz, 1H, CH (CH
3)
2), 3.34 (d, J=12.0Hz, 1H, B-CH-CH), 4.52 (d, J=12.0Hz, 1H, B-CH-CH), 5.63,5.81,5,97,5.99 (d, J=6.0Hz, 1H, C
6h
4), 6.37 (s, 1H, C=CH).
Example 1 gained one characterizes further containing multiple carborane group three core ruthenium duster compound crystal, and its process is as follows:
The crystal structure determination of duster compound: the monocrystalline choosing suitable size is placed on BrukerSMARTAPEXIICCD single crystal diffractometer, with graphite monochromatised MoK alpha-ray
for light source, at 291 (2) K temperature, collect diffraction data with ω/2 θ scan mode.Reduction of data SAINT program is carried out, and carries out absorption correction by SADABS program.The structure direct method of compound solves, and carries out the refine of complete matrix method of least squares to non-hydrogen atom coordinate and anisotropic temperature factor.Geometry hydrogenation.Structure elucidation adopts SHELXS-97, and structure refinement adopts SHELXL-97.Detailed axonometry data are in table 1; Important bond distance and bond angle data are in table 2; Crystalline structure is shown in accompanying drawing.
Can be seen by above-mentioned characterization result, duster compound crystal of the present invention belongs to oblique system, spacer P2
1/ c, molecular formula C
32h
66b
30oRu
3se
6cH
2cl
2h
2o, molecular weight=1671.06, unit cell parameters:
α=90 °, β=99.977 (3) °, γ=90 °,
z=4, R
1=0.0413, wR
2=0.0983.Its basic structure is the Ru atom being in central position is seven coordinations, and ligating atom is two (Se
2c
2b
10h
10)
2-group provides three Se atoms, (a Se
2c
2b
10h
9)
3-group provides two Se atoms and two Ru atoms from Metal-Metal bond, and these seven ligating atoms are being in the pentagonal bipyramid geometric configuration defining a distortion around the Ru atom of central position; Be in an extraneous metal Ru atom and still remain 6e neutral ligand p-Methylisopropylbenzene base, and the p-Methylisopropylbenzene base be connected with another metal Ru atom disappears due to the coordination of 1-ethynylcyclohexanol; With regard to bond distance, the distance of Ru-Ru metallic bond is respectively
belong to the bond distance of typical Ru-Ru singly-bound.
Above embodiment is only for illustration of content of the present invention, and in addition, the present invention also has other embodiment.But all employings are equal to replacement or the technical scheme that formed of equivalent deformation mode all drops in protection scope of the present invention.
The predominant crystal data of table 1 compound
The main bond distance of table 2 compound
with bond angle (°)
Claims (7)
1., containing a multiple carborane group three core ruthenium duster compound crystal, it is characterized in that: its molecular formula is C
32h
66b
30oRu
3se
6cH
2cl
2h
2o, molecular weight is 1671.06, and skeleton symbol is as follows
Described duster compound crystal belongs to oblique system, spacer P2
1/ c, unit cell parameters:
α=90 °, β=99.977 (3) °, γ=90 °,
z=4, R
1=0.0413, wR
2=0.0983.
2. as claimed in claim 1 a kind of containing multiple carborane group three core ruthenium duster compound crystal, it is characterized in that: the Ru atom being in central position is seven coordinations, ligating atom is two (Se
2c
2b
10h
10)
2-group provides three Se atoms, (a Se
2c
2b
10h
9)
3-group provides two Se atoms and two Ru atoms from Metal-Metal bond, and these seven ligating atoms are being in the pentagonal bipyramid geometric configuration defining a distortion around the Ru atom of central position; Be in an extraneous metal Ru atom and still remain 6e neutral ligand p-Methylisopropylbenzene base, and the p-Methylisopropylbenzene base be connected with another metal Ru atom disappears due to the coordination of 1-ethynylcyclohexanol; With regard to bond distance, the distance of Ru-Ru metallic bond is respectively
with
belong to the bond distance of typical Ru-Ru singly-bound.
3. a kind of preparation method containing multiple carborane group three core ruthenium duster compound crystal as claimed in claim 1, it is characterized in that: under argon shield, by 1,2-bis-carbon generation-enclosed-ten two carborane is dissolved in anhydrous diethyl ether, add n-Butyl Lithium, selenium powder successively, after stirring and dissolving, dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimeric tetrahydrofuran solution will be dissolved with and add, temperature control 0 DEG C, stirring reaction 4 hours final vacuums drain solvent; Use methylene dichloride lysate, add 1-ethynylcyclohexanol, temperature control 20-25 DEG C, stirring reaction 23-24 hour, reaction solution is concentrated into dry; The mixed solution of sherwood oil and methylene dichloride is eluent, crosses the separation of 200-300 order silicagel column and obtains target duster compound; Carry out crystallization with the mixed solvent of sherwood oil and methylene dichloride, obtain yellow bulk crystals.
4. a kind of preparation method containing multiple carborane group three core ruthenium duster compound crystal as claimed in claim 3, is characterized in that: the volume ratio of organic solvent anhydrous diethyl ether, tetrahydrofuran (THF) and methylene dichloride that reaction system uses is 1: 2: 1.
5. a kind of preparation method containing multiple carborane group three core ruthenium duster compound crystal as claimed in claim 3, it is characterized in that: the mol ratio of described 1,2-bis-carbon generation-enclosed-ten two carborane, n-Butyl Lithium, selenium powder, dichloro (p-Methylisopropylbenzene base) ruthenium (II) dimer and 1-ethynylcyclohexanol is 3: 6: 9: 2: 2.
6. a kind of preparation method containing multiple carborane group three core ruthenium duster compound crystal as claimed in claim 3, is characterized in that: described eluent by sherwood oil and methylene dichloride by 2: 1 volume ratio mixture form.
7. a kind of preparation method containing multiple carborane group three core ruthenium duster compound crystal as claimed in claim 3, is characterized in that: the mixed solvent that crystallization uses by sherwood oil and methylene dichloride by 1: 1 volume ratio mixture form.
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Non-Patent Citations (4)
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| A Novel Dinuclear Ruthenium(I)/Ruthenium(III) Half-Sandwich Complex Containing Two Chelating 1,2-Dicarba-closo-dodecaborane-1,2-dithiolate Ligands and Its Reactivity with Alkynes;De-Hong Wu et al.;《Organometallics》;20070228;第26卷(第7期);第1560—1562页 * |
| BeH bond activation half-sandwich Ir and Ru complexes containing carboranylamidinate selenolate ligands;Zi-Jian Yao et al.;《Journal of Organometallic Chemistry》;20121231;第721—722卷;第31—35页 * |
| Diruthenium Half-Sandwich Complexes Containing One μ-E2 （E= S，Se） Unit and Two Chelating 1,2-Dicarba-closo-dodecaborane-1,2-dithiolate Ligands: Reactivity Studies with Methyl Acetylene Carboxylates;De-Hong Wu et al.;《Organometallics》;20071107;第26卷(第25期);第6300—6306页 * |
| Mixed-Valent Diruthenium Half-Sandwich Complexes Containing Two Chelating 1，2-Dicarba-closo-dodecaborane-1，2-dithiolate Ligands： Reactivity towards Phenylacetylene，1，4-Diethynylbenzene，and Ethynylferrocene;Dehong Wu et al.;《Inorganic Chemistry》;20080603;第47卷(第14期);第6524—6531页 * |
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