CN104402930B - A kind of symmetry benzimidazole ruthenium complex and preparation method thereof - Google Patents
A kind of symmetry benzimidazole ruthenium complex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of symmetry benzimidazole ruthenium complex and preparation method thereof, belong to synthesising chemical technology field, this preparation method is with 2,4,6-trisbromomethyl trimethylbenzene and triethyl phosphate are initiation material, using two-step method synthesis fixed ligands, this fixed ligands is last synthesizes target product with three aquation rutheniums under microwave condition.The present invention designs the symmetry benzimidazole ruthenium complex of synthesis and has excellent stability and optical, electrical chemical property, the symmetrical phosphate in its molecule two ends can be with the electrically-conductive backing plate surface effect by covalent bond such as ITO, make this symmetry benzimidazole ruthenium complex molecule be fixed on such electrically-conductive backing plate and realize LBL self-assembly, be a kind of excellent light-sensitive coloring agent.Additionally, the design building-up process of this symmetry benzimidazole ruthenium complex is simple, with low cost, Microwave-assisted synthesis technology is quickly, efficiently.
Description
Technical field
The present invention relates to a kind of symmetry benzimidazole ruthenium complex and preparation method thereof, belong to synthesising chemical technology neck
Territory.
Background technology
In recent years, increasing researcher starts each metal ion species (main group metal, transition metal and rare earth gold
Belong to) it is incorporated in organic compound so that great changes will take place for the optical physics of system and chemical property.This type of complex not only has
There is the good luminous performance of metal complex, had the material property that organic compound itself is excellent simultaneously concurrently, be greatly expanded
This kind of material is in the application in the fields such as sun conversion, Journal of Molecular Catalysis, luminescence, information storage.
Owing to ruthenium complex has, thermodynamic stability is good, photochemical light physical message abundant, excited state reaction activity is high
With the characteristic such as life-span length and luminescent properties are good, chemiluminescence, electro transfer, nonlinear optics material the most it are widely used in
Material, molecular light switch, molecular recognition, sensor, DSSC and the field such as photocatalytic degradation water and organic matter
Research.Obvious MLCT peak, good Optical Electro-Chemistry part matter and the oxidation of high stable is had at visible region based on ruthenium complex
State and be considered as maximally effective sensitizer.It is generally believed that as Ru (bpy)3 2+Can carry during with ester group linkage electron donor
The high utilization ratio to light.Fine application prospect based on dye-sensitized solar cells, a lot of research workers are still devoted to
Obtain the research of the more preferable sensitizer of sensitization effect.Can prepare after changing different ligands due to ruthenium complex and there is difference
The novel complexes of characteristic, so this series complex has the biggest research space, utilize the abundant photochemistry of ruthenium complex and
Electrochemical properties, develops its application in dye-sensitized solar cells field and has important theoretical and practical significance.
Under conditions of microwave, utilize it to heat the advantages such as quick, homogeneous and selectivity, be applied to modern organic synthesis and grind
Technology in studying carefully, referred to as microwave synthesis.Research in microwave assisted organic reaction is a focus in organic chemistry filed.Borrow
Helping microwave technology, the heating means that the reaction speed of organic reaction is more traditional can improve the most thousands of times of decades of times, Er Qiecao
Make simplicity, productivity height, easy purification of products, safety and sanitation, thus promote developing rapidly so that microwave organic reaction.
The research of the most domestic preparation method to utilizing microwave synthesis symmetry benzimidazole ruthenium complex yet there are no
Report.The method of the preparation of disclosed ruthenium complex mainly has:
The Chinese patent of Publication No. CN 103408597 A disclosed " a kind of Aromatic ruthenium complex and synthetic method thereof "
In, synthesizing a kind of Aromatic ruthenium complex with aromatic hydrocarbons ruthenous chloride dimer, this ruthenium complex has anticancer cooperative effect, to cancer
Cell has certain inhibitory action.
The Chinese patent of Publication No. CN 102617647 A disclosed " terpyridyl ruthenium complex, preparation method and
Its application " in, give electron donor ligand with thiocyanic acid for strong, carboxyl bipyridyl is the part containing adsorption group, terpyridyl derivative
Having synthesized terpyridyl ruthenium complex for assistant ligand, this complex is applied to dye sensitization sun electricity as light-sensitive coloring agent
Pond.
The Chinese patent of Publication No. CN 102391309 A disclosed " Ru-polypyridine complex and the synthesis of derivative thereof
Method " in, by many from the company of different the position of substitution, different ligands type for ruthenium source material pyridine ligands, a step or be divided into some steps
Suddenly, in the closed reactor of pressurized, heated, reaction obtains target product, the high pressure of the Ru-polypyridine complex that this invention provides
Synthetic method requires height to reactor.
The synthetic method of the most conventional ruthenium complex is typically with ruthenium source materials such as ruthenium trichlorides as initiation material, often
Under the conditions of pressure, carry out complex reaction several times by being heated to reflux mode, obtain the complex between specific part and ruthenium, generally
Synthesis ruthenium complex procedure is numerous and diverse, time length and purification of products exist bigger difficulty.
Summary of the invention
The problem existed for above-mentioned prior art and deficiency, the present invention provides a kind of symmetry benzimidazole ruthenium to coordinate
Thing, this ruthenium complex phosphate group symmetrical using two ends is as fixed ligands, 3 N on the imidazole ring of benzimidizole derivatives
Atom forms complex with metal Ru ion coordination, and its chemical structural formula is as follows:
。
The symmetry benzimidazole ruthenium complex that the present invention provides has excellent stability and optical, electrical chemical property,
The symmetrical phosphate in its molecule two ends can make this symmetry benzo miaow with the electrically-conductive backing plate surface effect by covalent bond such as ITO
Azole ruthenium complex molecule is fixed on such electrically-conductive backing plate and realizes LBL self-assembly, is a kind of excellent light-sensitive coloring agent.
Another object of the present invention there are provided the preparation method of a kind of symmetry benzimidazole ruthenium complex, specifically interior
Hold as follows:
(1) in the reactor by 2,4,6-trisbromomethyl trimethylbenzenes are dissolved in meta-xylene, simultaneously by tricresyl phosphate second
Ester is dissolved in meta-xylene and instills in reactor, stirs reaction 20 ~ 30h, use post after decompression distillation at 90 ~ 120 DEG C
Chromatography purifies and obtains 1-bromomethyl-3,5-bis-(diethyl phosphonate methyl)-2,4,6-trimethylbenzenes, wherein 2,4,6-tribromo
Methyl trimethoxy base benzene is 1:2 ~ 3 with the mol ratio of triethyl phosphate；
(2) under inert gas atmosphere, the NaH after pentane washs is suspended in dry DMF, is subsequently adding 2,6-
Two [2-benzimidazolyl] pyridine, is dropwise added drop-wise to the 1-bromine first being dissolved in DMF after being heated to 70 ~ 90 DEG C of stirring 10 ~ 15h
Base-3,5-bis-(diethyl phosphonate methyl)-2, in 4,6-trimethylbenzene solution, it is heated to 70 ~ 90 DEG C of stirring 20 ~ 26h, cooling
Rear addition methyl alcohol, uses column chromatography to purify after decompression distillation and obtains part 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl
Base phosphonate ester Methyl-benzvl)-2-benzimidazolyl) pyridine, wherein 2,6-bis-[2-benzimidazolyl] pyridine and 1-bromine first
The mol ratio of base-3,5-two (diethyl phosphonate methyl)-2,4,6-trimethylbenzene is 1:2 ~ 3；
(3) under inert gas atmosphere, by RuCl3•3H2O is dissolved in glycerin solution, and what addition step (2) obtained joins
Body 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl phosphonate Methyl-benzvl)-2-benzimidazolyl) pyridine, microwave adds
Isothermal reaction 1 ~ 3min after hot to 240 ~ 290 DEG C, adds the KPF of excess after being cooled to room temperature6It is poured into after solution in water, generation
Solid obtains complex intermediate, wherein RuCl through filtering, wash, using sephadex exclusion chromatography to purify after drying3•
3H2O and part 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl phosphonate Methyl-benzvl)-2-benzimidazolyl) pyridine
Mol ratio be 1:2 ~ 3；
(4) under inert gas atmosphere, the complex intermediate that step (3) obtains is dissolved in anhydrous DMF solution,
Dropping Me3SiBr solution, adds the MeOH of excess after being stirred at room temperature 45 ~ 60h, reducing pressure after continuing stirring 10 ~ 15h evaporates
MeOH and DMF, is dissolved in ammoniacal liquor after MeCN washs, and adds excess KPF6Solution, with acid for adjusting pH value until producing purple and sinking
Form sediment, filter and i.e. obtain symmetry benzimidazole ruthenium complex, wherein complex intermediate and Me3The mol ratio of SiBr be 1:250 ~
500。
The described ruthenium in symmetry benzimidazole ruthenium complex is II valency.
The method that above-mentioned symmetry benzimidazole ruthenium complex utilizes microwave to prepare, the reaction equation of step (1) is as follows:
The reaction equation of step (2) is as follows:
The reaction equation of step (3) is as follows:
The reaction equation of step (4) is as follows:
。
The advantage of preparation method is to use microwave process for synthesizing to prepare symmetry benzimidazole ruthenium complex, has heating
Speed is fast, heat utilization rate is high, be quick on the draw and product quality high.Compared with traditional ruthenium complex preparation method,
Microwave can make temperature of reaction system raise rapidly at short notice, thus shortens the reaction time, reduces the life of side reaction
Become, and improve the conversion ratio of reaction.
The invention has the beneficial effects as follows:
1, the present invention uses microwave process for synthesizing to prepare symmetry benzimidazole ruthenium complex, has firing rate fast, hot
Can utilization rate be high, be quick on the draw and product quality high.Compared with traditional ruthenium complex preparation method, microwave energy
Enough make temperature of reaction system raise rapidly at short notice, thus shorten the reaction time, reduce the generation of side reaction, and improve
The conversion ratio of reaction and target product purity.
2, the symmetry benzimidazole ruthenium complex that the present invention prepares has three tooth chelating and the features of high stability,
Added value of product is high.Preparation process i.e. can reach being easily-synthesized and modifying of object, process control by simple operations
And pollution-free, raw material is easy to get, with low cost.
3, the complex that the present invention obtains has excellent stability and optical, electrical chemical property, in this complex molecule
The symmetrical phosphate group in two ends can make this symmetry benzimidazole with the electrically-conductive backing plate surface effect by covalent bond such as ITO
Ruthenium complex molecule is fixed on such electrically-conductive backing plate and realizes LBL self-assembly, is a kind of excellent light-sensitive coloring agent.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to described
Content.
Embodiment 1: symmetry benzimidazole ruthenium complex, it is characterised in that: this ruthenium complex is with the phosphorus of two ends symmetry
Acid groups is as fixed ligands, and 3 atom N on the imidazole ring of benzimidizole derivatives are formed with metal Ru ion coordination and coordinate
Thing, its chemical structural formula is as follows:
。
The preparation method of above-mentioned symmetry benzimidazole ruthenium complex specifically comprises the following steps that
(1) synthetic ligands 1-bromomethyl-3,5-bis-(diethyl phosphonate methyl)-2,4,6-trimethylbenzenes, it is designated as PO
(OEt)2Br
Dissolve the 2 of 5g, 12.53mmol, 4,6-trisbromomethyl trimethylbenzenes in the reactor in the meta-xylene of 25ml,
By the triethyl phosphate of 4.57g, 25.06mmol (2,4,6-trisbromomethyl trimethylbenzenes are 1 with the mol ratio of triethyl phosphate:
2) instilling after being dissolved in the meta-xylene of 25ml in reactor, after adding thermal agitation 20h at 90 DEG C, decompression is distilled off solvent
Obtaining crude product, the purification of gained crude product uses column chromatography, the fixing spherical silica gel using 63 ~ 210 μm mutually, fixes mutually straight
Footpath be 7.5cm highly for 5cm, flowing is EtOAc solution mutually, carries out purification through column chromatography and obtains light yellow product PO (OEt)2Br.MS (MALDI-TOF, CH2Cl2): m/z=400.64, [M] calculated value is 400.9922, wherein M=C12H19BrO6P2。1H-
NMR(500MHz, CDCl3): δ (ppm)=4.69 (2H, s), 3.96 (8H, m), 3.38 (4H, d, J=12.7Hz), 2.63 (3H,
S), 2.49 (6H, s), 1.22 (12H, t, J=7.5Hz).
(2) synthetic ligands 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl phosphonate Methyl-benzvl)-2-benzo miaow
Oxazolyl) pyridine, it is designated as XPOEt
In a nitrogen atmosphere, the NaH of 1.08g, 27.12mmol, 30% after pentane washs is suspended in 20ml anhydrous
In DMF, the 2 of addition 1.78g, 5.71mmol, 6-bis-[2-benzimidazolyl] pyridine, at 70 DEG C, add thermal agitation 10h, in this phase
Between suspension gradually dissolve obtain clarification yellow solution, reactant liquor is transferred in constant pressure funnel, the most dropwise
The PO (OEt) that the 5.84g, 11.42mmol step (2) being added drop-wise to be dissolved in 15ml DMF obtains2Br(2,6-bis-[2-benzene
And imidazole radicals] pyridine and PO (OEt)2The mol ratio of Br is 1:2) in, at 70 DEG C, add thermal agitation 20h, add after being cooled to room temperature
Entering the methyl alcohol of 3ml, decompression is distilled off solvent and obtains white crude.The crude product of gained uses column chromatography to purify, fixing
Using the spherical silica gel of 63 ~ 210um mutually, fixing mutually a diameter of 7.5cm is highly 6cm, and flowing is acetone soln mutually, through column chromatography
Method carries out purification and obtains yellow product XPOEt.MS (MALDI-TOF, CH2Cl2): m/z=1176.19, [M] calculated value is
1176.4922, wherein M=C59H81N5O12P4。1H-NMR(500MHz, CDCl3): δ (ppm)=8.47 (2H, d, J=8.5Hz),
8.19 (1H, t, J=7.2Hz), 7.79 (2H, d, J=7.3Hz), 7.13 (2H, t, J=7.9Hz), 6.96 (2H, t, J=7.7Hz),
6.78 (2H, d, J=8.9Hz), 6.12 (4H, s), 3.95-3.86 (16H, m), 3.27 (8H, d, J=22.2Hz), 2.74 (6H,
S), 2.20 (12H, s), 1.12 (24H, t, J=7.64Hz).
(3) synthetic compound intermediate [Ru (XPOEt)2] (PF6)2: before experiment, take 0.26g, 1.25mmol's
RuCl3•3H2O carries out being vacuum dried 0.5h, during experiment in a nitrogen atmosphere, the RuCl that will be dried3•3H2O is dissolved in 25ml's
In glycerin solution, add the XPOEt(RuCl that 2.94g, 2.5mmol step (2) obtain3•3H2The mol ratio of O with XPOEt is
1:2), isothermal reaction 3min after heating using microwave to 250 DEG C, the solution obtained is cooled to room temperature, adds the KPF of excess6After solution
Being poured in water, the solid obtained is through filtering, obtaining purple crude product after drying.The purification of gained crude product uses sephadex
Exclusion chromatography, the fixing Sephadex LH-20 that uses mutually, fixing mutually a diameter of 3cm is highly 15cm, and flowing is 50/50 mutually
MeOH/ MeCN solution, obtains purple complex intermediate [Ru (XPOEt) after exclusion chromatography purifies2] (PF6)2。1H-
NMR(500MHz, CDCl3): δ (ppm)=8.79 (4H, d, J=8.2Hz), 8.47 (2H, t, J=7.7Hz), 7.92 (4H, d, J=
7.1Hz), 7.22 (4H, t, J=7.6Hz), 6.59 (4H, m), 6.41 (4H, d, J=8.1Hz), 6.05 (8H, s), 4.36-3.98
(32H, m), 3.53 (16H, d, J=22.2Hz), 2.85 (12H, s), 2.33 (24H, s), 1.28 (48H, m).
(4) synthesis symmetry benzimidazole ruthenium complex, is labeled as [Ru (XPOH)2] (PF6)2
In a nitrogen atmosphere, by [the Ru (XPOEt) of 1.96g, 0.80mmol2] (PF6)2It is dissolved into the dry DMF of 80ml
In solution, drip 31.84g in three times, the Me of 27.45ml, 208mmol3SiBr solution ([Ru2(tpyPOEt)2] (PF6)2With
Me3The mol ratio of SiBr is 1:260), dropping interval 30min, adds the MeOH of 15ml after being stirred at room temperature 45 hours every time,
After being stirred at room temperature 10 hours, decompression evaporates MeOH and DMF, is dissolved in ammoniacal liquor after MeCN washs, and adds excess KPF6Molten
Liquid, with hydrochloric acid regulation pH value until producing purple precipitation, filtering and i.e. obtaining purple product [Ru (XPOH)2] (PF6)2。1H-NMR
(500MHz, DMSO-d6): δ (ppm)=8.73 (4H, d, J=8.9Hz), 8.42 (2H, t, J=7.9Hz), 7.96 (4H, d, J=
7.3Hz), 7.27 (4H, t, J=7.0Hz), 6.52 (4H, m), 6.44 (4H, d, J=8.8Hz), 6.13 (8H, s), 3.57 (16H,
D, J=20.3Hz), 2.80 (12H, s), 2.27 (24H, s).
Above-mentioned [the Ru (XPOH) prepared2] (PF6)2, molecular formula is as follows:
。
Embodiment 2: symmetry benzimidazole ruthenium complex, it is characterised in that: this ruthenium complex is with the phosphorus of two ends symmetry
Acid groups is as fixed ligands, and 3 atom N on the imidazole ring of benzimidizole derivatives are formed with metal Ru ion coordination and coordinate
Thing, its chemical structural formula is as follows:
。
The preparation method of above-mentioned symmetry benzimidazole ruthenium complex specifically comprises the following steps that
(1) synthetic ligands 1-bromomethyl-3,5-bis-(diethyl phosphonate methyl)-2,4,6-trimethylbenzenes, it is designated as PO
(OEt)2Br
Dissolve the 2 of 4.2g, 10.53mmol, 4, the 6-trisbromomethyl trimethylbenzenes meta-xylene to 23ml in the reactor
In, by the triethyl phosphate of 4.22g, 23.16mmol, (2,4,6-trisbromomethyl trimethylbenzenes with the mol ratio of triethyl phosphate are
Instilling after 1:2.2) being dissolved in the meta-xylene of 23ml in reactor, after adding thermal agitation 24h at 100 DEG C, decompression is distilled off
Solvent obtains crude product.The purification of gained crude product uses column chromatography, the fixing spherical silica gel using 63 ~ 210um mutually, fixes
Mutually a diameter of 7.5cm is highly 5cm, and flowing is EtOAc solution mutually, carries out purification through column chromatography and obtains light yellow product PO
(OEt)2Br.MS (MALDI-TOF, CH2Cl2): m/z=400.23, [M] calculated value is 400.9922, wherein M=
C12H19BrO6P2。1H-NMR(500MHz, CDCl3): δ (ppm)=4.63 (2H, s), 3.97 (8H, m), 3.34 (4H, d, J=
12.7Hz), 2.69 (3H, s), 2.41 (6H, s), 1.28 (12H, t, J=7.2Hz).
(2) synthetic ligands 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl phosphonate Methyl-benzvl)-2-benzo miaow
Oxazolyl) pyridine, it is designated as XPOEt
In a nitrogen atmosphere, the NaH of 0.75g, 18.7mmol, 30% after pentane washs is suspended in 15ml anhydrous
In DMF, the 2 of addition 1.23g, 3.94mmol, 6-bis-[2-benzimidazolyl] pyridine, at 80 DEG C, add thermal agitation 12h, in this phase
Between suspension gradually dissolve obtain clarification yellow solution, reactant liquor is transferred in constant pressure funnel, the most dropwise
What the 5.04g, 9.85mmol step (2) being added drop-wise to be dissolved in 12ml DMF obtained PO (OEt)2Br(2,6-bis-[2-
Benzimidazolyl] pyridine and PO (OEt)2The mol ratio of Br is 1:2.5) in, at 80 DEG C, add thermal agitation 23h, be cooled to room temperature
The methyl alcohol of rear addition 3ml, decompression is distilled off solvent and obtains white crude.The crude product of gained uses column chromatography to purify,
The fixing spherical silica gel using 63 ~ 210um mutually, fixing mutually a diameter of 7.5cm is highly 6cm, and flowing is acetone soln mutually, through post
Chromatography carries out purification and obtains yellow product XPOEt.MS (MALDI-TOF, CH2Cl2): m/z=1176.64, [M] calculated value is
1176.4922, wherein M=C59H81N5O12P4。1H-NMR(500MHz, CDCl3): δ (ppm)=8.41 (2H, d, J=8.8Hz),
8.12 (1H, t, J=7.6Hz), 7.73 (2H, d, J=7.5Hz), 7.18 (2H, t, J=7.2Hz), 6.94 (2H, t, J=7.6Hz),
6.73 (2H, d, J=8.1Hz), 6.17 (4H, s), 3.98-3.82 (16H, m), 3.22 (8H, d, J=22.7Hz), 2.75 (6H,
S), 2.28 (12H, s), 1.18 (24H, t, J=7.52Hz).
(3) complex intermediate [Ru (XPOEt)2] (PF6)2Synthesis: before experiment, take 0.15g, 0.72mmol's
RuCl3•3H2O carries out being vacuum dried 0.5h, during experiment in a nitrogen atmosphere, the RuCl that will be dried3•3H2O is dissolved in 25ml's
In glycerin solution, add the XPOEt(RuCl that 2.12g, 1.8mmol step (2) obtain3•3H2The mol ratio of O with XPOEt is
1:2.5), isothermal reaction 2min after heating using microwave to 270 DEG C, the solution obtained is cooled to room temperature, adds the KPF of excess6Solution
After be poured in water, the solid obtained is through filtering, obtaining purple crude product after drying.The purification of gained crude product uses glucan to coagulate
Glue gel chromatography, the fixing Sephadex LH-20 that uses mutually, fixing mutually a diameter of 3cm is highly 15cm, and flowing is 50/50 mutually
MeOH/ MeCN solution, through exclusion chromatography purify after obtain purple complex intermediate [Ru (XPOEt)2] (PF6)2。1H-NMR(500MHz, CDCl3): δ (ppm)=8.82 (4H, d, J=8.5Hz), 8.32 (2H, t, J=7.2Hz), 7.97 (4H, d,
J=7.3Hz), 7.28 (4H, t, J=7.1Hz), 6.55 (4H, m), 6.42 (4H, d, J=8.6Hz), 6.01 (8H, s), 4.33-
3.94 (32H, m), 3.57 (16H, d, J=22.6Hz), 2.82 (12H, s), 2.37 (24H, s), 1.23 (48H, m).
(4) synthesis symmetry benzimidazole ruthenium complex, is labeled as [Ru (XPOH)2] (PF6)2
In a nitrogen atmosphere, by [the Ru (XPOEt) of 1.27g, 0.52mmol2] (PF6)2It is dissolved into the dry DMF of 70ml
In solution, drip 27.86g in three times, the Me of 24.02ml, 182mmol3SiBr solution ([Ru2(tpyPOEt)2] (PF6)2With
Me3The mol ratio of SiBr is 1:350), dropping interval 30min, adds the MeOH of 15ml after being stirred at room temperature 48 hours every time,
After being stirred at room temperature 12 hours, decompression evaporates MeOH and DMF, is dissolved in ammoniacal liquor after MeCN washs, and adds excess KPF6Molten
Liquid, with hydrochloric acid regulation pH value until producing purple precipitation, filtering and i.e. obtaining purple product [Ru (XPOH)2] (PF6)2。1H-NMR
(500MHz, DMSO-d6): δ (ppm)=8.77 (4H, d, J=8.0Hz), 8.44 (2H, t, J=6.4Hz), 7.93 (4H, d, J=
7.9Hz), 7.23 (4H, t, J=6.3Hz), 6.58 (4H, m), 6.39 (4H, d, J=8.1Hz), 6.24 (8H, s), 3.50 (16H,
D, J=18.9Hz), 2.81 (12H, s), 2.20 (24H, s).
Embodiment 3: symmetry benzimidazole ruthenium complex, it is characterised in that: this ruthenium complex is with the phosphorus of two ends symmetry
Acid groups is as fixed ligands, and 3 atom N on the imidazole ring of benzimidizole derivatives are formed with metal Ru ion coordination and coordinate
Thing, its chemical structural formula is as follows:
。
The preparation method of above-mentioned symmetry benzimidazole ruthenium complex specifically comprises the following steps that
(1) synthetic ligands 1-bromomethyl-3,5-bis-(diethyl phosphonate methyl)-2,4,6-trimethylbenzenes, it is designated as PO
(OEt)2Br
Dissolve the 2 of 3.5g, 8.77mmol, 4, the 6-trisbromomethyl trimethylbenzenes meta-xylene to 20ml in the reactor
In, by the triethyl phosphate of 4.47g, 24.56mmol, (2,4,6-trisbromomethyl trimethylbenzenes with the mol ratio of triethyl phosphate are
Instilling after 1:2.8) being dissolved in the meta-xylene of 20ml in reactor, after adding thermal agitation 30h at 120 DEG C, decompression is distilled off
Solvent obtains crude product.The purification of gained crude product uses column chromatography, the fixing spherical silica gel using 63 ~ 210um mutually, fixes
Mutually a diameter of 7.5cm is highly 5cm, and flowing is EtOAc solution mutually, carries out purification through column chromatography and obtains light yellow product PO
(OEt)2Br.MS (MALDI-TOF, CH2Cl2): m/z=400.84, [M] calculated value is 400.9922, wherein M=
C12H19BrO6P2。1H-NMR(500MHz, CDCl3): δ (ppm)=4.59 (2H, s), 3.92 (8H, m), 3.41 (4H, d, J=
12.5Hz), 2.64 (3H, s), 2.45 (6H, s), 1.29 (12H, t, J=7.4Hz).
(2) synthetic ligands 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl phosphonate Methyl-benzvl)-2-benzo miaow
Oxazolyl) pyridine, it is designated as XPOEt
In a nitrogen atmosphere, the NaH of 0.48g, 11.97mmol, 30% after pentane washs is suspended in 10ml anhydrous
In DMF, the 2 of addition 0.78g, 2.52mmol, 6-bis-[2-benzimidazolyl] pyridine, at 90 DEG C, add thermal agitation 15h, in this phase
Between suspension gradually dissolve obtain clarification yellow solution, reactant liquor is transferred in constant pressure funnel, the most dropwise
What the 3.87g, 7.55mmol step (2) being added drop-wise to be dissolved in 10ml DMF obtained PO (OEt)2Br(2,6-bis-[2-
Benzimidazolyl] pyridine and PO (OEt)2The mol ratio of Br is 1:3) in, at 90 DEG C, add thermal agitation 26h, after being cooled to room temperature
Adding the methyl alcohol of 3ml, decompression is distilled off solvent and obtains white crude.The crude product of gained uses column chromatography to purify, Gu
The fixed spherical silica gel using 63 ~ 210um mutually, fixing mutually a diameter of 7.5cm is highly 6cm, and flowing is acetone soln mutually, through post look
Spectrometry carries out purification and obtains yellow product XPOEt.MS (MALDI-TOF, CH2Cl2): m/z=1176.61, [M] calculated value is
1176.4922, wherein M=C59H81N5O12P4。1H-NMR(500MHz, CDCl3): δ (ppm)=8.40 (2H, d, J=8.5Hz),
8.18 (1H, t, J=7.1Hz), 7.79 (2H, d, J=7.2Hz), 7.22 (2H, t, J=7.7Hz), 6.80 (2H, t, J=
7.4Hz), 6.70 (2H, d, J=8.8Hz), 6.24 (4H, s), 3.95-3.78 (16H, m), 3.23 (8H, d, J=22.4Hz),
2.79 (6H, s), 2.22 (12H, s), 1.15 (24H, t, J=7.50Hz).
(3) synthetic compound intermediate [Ru (XPOEt)2] (PF6)2Synthesis: before experiment, take 0.07g, 0.36mmol
RuCl3•3H2O carries out being vacuum dried 0.5h, during experiment in a nitrogen atmosphere, the RuCl that will be dried3•3H2O is dissolved in 20ml
Glycerin solution in, add 1.27g, 1.08mmol step (2) XPOEt(RuCl that obtains3•3H2The mol ratio of O Yu XPOEt
For 1:3), isothermal reaction 1min after heating using microwave to 290 DEG C, the solution obtained is cooled to room temperature, adds the KPF of excess6Solution
After be poured in water, the solid obtained is through filtering, obtaining purple crude product after drying.The purification of gained crude product uses glucan to coagulate
Glue gel chromatography, the fixing Sephadex LH-20 that uses mutually, fixing mutually a diameter of 3cm is highly 15cm, and flowing is 50/50 mutually
MeOH/ MeCN solution, through exclusion chromatography purify after obtain purple complex intermediate [Ru (XPOEt)2] (PF6)2。1H-NMR(500MHz, CDCl3): δ (ppm)=8.86 (4H, d, J=8.2Hz), 8.43 (2H, t, J=7.9Hz), 7.90 (4H, d,
J=6.5Hz), 7.31 (4H, t, J=7.9Hz), 6.57 (4H, m), 6.40 (4H, d, J=8.1Hz), 6.11 (8H, s), 4.30-
3.97 (32H, m), 3.51 (16H, d, J=21.4Hz), 2.77 (12H, s), 2.32 (24H, s), 1.29 (48H, m).
(4) synthesis symmetry benzimidazole ruthenium complex, is labeled as [Ru (XPOH)2] (PF6)2
In a nitrogen atmosphere, by [the Ru (XPOEt) of 1.13g, 0.46mmol2] (PF6)2It is dissolved into the dry DMF of 60ml
In solution, drip 31.68g in three times, the Me of 27.32ml, 207mmol3SiBr solution ([Ru2(tpyPOEt)2] (PF6)2With
Me3The mol ratio of SiBr is 1:450), dropping interval 30min, adds the MeOH of 15ml after being stirred at room temperature 60 hours every time,
After being stirred at room temperature 15 hours, decompression evaporates MeOH and DMF, is dissolved in ammoniacal liquor after MeCN washs, and adds excess KPF6Molten
Liquid, with hydrochloric acid regulation pH value until producing purple precipitation, filtering and i.e. obtaining purple product [Ru (XPOH)2] (PF6)2。1H-NMR
(500MHz, DMSO-d6): δ (ppm)=8.70 (4H, d, J=7.5Hz), 8.39 (2H, t, J=6.9Hz), 7.89 (4H, d, J=
7.7Hz), 7.29 (4H, t, J=6.1Hz), 6.63 (4H, m), 6.47 (4H, d, J=9.3Hz), 6.20 (8H, s), 3.53 (16H,
D, J=19.4Hz), 2.84 (12H, s), 2.21 (24H, s).
Above the detailed description of the invention of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party
Formula, in the ken that those of ordinary skill in the art are possessed, it is also possible to make on the premise of without departing from present inventive concept
Go out various change.
Claims (2)
1. a symmetry benzimidazole ruthenium complex, it is characterised in that: this ruthenium complex is with the phosphate group of two ends symmetry
As fixed ligands, 3 atom N on the imidazole ring of benzimidizole derivatives form complex with metal Ru ion coordination, its
Chemical structural formula is as follows:
。
2. the preparation method of the symmetry benzimidazole ruthenium complex described in claim 1, it is characterised in that concrete steps are such as
Under:
(1) in the reactor by 2,4,6-trisbromomethyl trimethylbenzenes are dissolved in meta-xylene, simultaneously that triethyl phosphate is molten
Solution is in meta-xylene and instills in reactor, stirs reaction 20 ~ 30h, use column chromatography after decompression distillation at 90 ~ 120 DEG C
Method purifies and obtains 1-bromomethyl-3,5-bis-(diethyl phosphonate methyl)-2,4,6-trimethylbenzenes, wherein 2,4,6-trisbromomethyl
Trimethylbenzene is 1:2 ~ 3 with the mol ratio of triethyl phosphate；
(2) under inert gas atmosphere, the NaH after pentane washs is suspended in dry DMF, is subsequently adding 2,6-bis-
[2-benzimidazolyl] pyridine, is dropwise added drop-wise to the 1-bromine first being dissolved in DMF after being heated to 70 ~ 90 DEG C of stirring 10 ~ 15h
Base-3,5-bis-(diethyl phosphonate methyl)-2, in 4,6-trimethylbenzene solution, it is heated to 70 ~ 90 DEG C of stirring 20 ~ 26h, cooling
Rear addition methyl alcohol, uses column chromatography to purify after decompression distillation and obtains part 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl
Base phosphonate ester Methyl-benzvl)-2-benzimidazolyl) pyridine, wherein 2,6-bis-[2-benzimidazolyl] pyridine and 1-bromine first
The mol ratio of base-3,5-two (diethyl phosphonate methyl)-2,4,6-trimethylbenzene is 1:2 ~ 3；
(3) under inert gas atmosphere, by RuCl3•3H2O is dissolved in glycerin solution, adds the part 2 that step (2) obtains,
6-bis-(N-(2,4,6-methyl-3,5-diethyl phosphonate Methyl-benzvl)-2-benzimidazolyl) pyridine, heating using microwave is extremely
Isothermal reaction 1 ~ 3min after 240 ~ 290 DEG C, adds the KPF of excess after being cooled to room temperature6It is poured into after solution in water, the solid of generation
Complex intermediate, wherein RuCl is obtained through filtering, wash, using sephadex exclusion chromatography to purify after drying3•3H2O
With rubbing of part 2,6-bis-(N-(2,4,6-methyl-3,5-diethyl phosphonate Methyl-benzvl)-2-benzimidazolyl) pyridine
That ratio is 1:2 ~ 3, and complex intermediate structure formula is as follows:
；
(4) under inert gas atmosphere, the complex intermediate that step (3) obtains is dissolved in anhydrous DMF solution, dropping
Me3SiBr solution, adds the MeOH of excess after being stirred at room temperature 45 ~ 60h, continue decompression after stirring 10 ~ 15h evaporate MeOH and
DMF, is dissolved in ammoniacal liquor after MeCN washs, and adds excess KPF6Solution, with acid for adjusting pH value until producing purple precipitation, filters
Obtain symmetry benzimidazole ruthenium complex, wherein complex intermediate and Me3The mol ratio of SiBr is 1:250 ~ 500.
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