CN103159799B - Nitrogen heterocyclic carbene complex of rhodium and preparation method thereof - Google Patents
Nitrogen heterocyclic carbene complex of rhodium and preparation method thereof Download PDFInfo
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- CN103159799B CN103159799B CN201310109297.0A CN201310109297A CN103159799B CN 103159799 B CN103159799 B CN 103159799B CN 201310109297 A CN201310109297 A CN 201310109297A CN 103159799 B CN103159799 B CN 103159799B
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Abstract
The invention relates to a nitrogen heterocyclic carbene complex of rhodium, and the chemical formula is as follows, wherein n is 3 or 4. The nitrogen heterocyclic carbene complex of the rhodium, disclosed by the invention expands the structural diversity of the complex of the rhodium and increases a member with novel structure for a complex family of the rhodium. The complex is a good catalyst and environment-friendly, and further has extensive application prospects. The method has the advantages of mild reaction conditions, simple post-treatment and higher yield (preferably 75%), and a simple and easy way is provided for low-cost synthesis of a binuclear rhodium complex containing a bidentate carbene ligand.
Description
Technical field
The invention belongs to Organometallic Chemistry technical field, be specifically related to double-core silver carbene complex and bicyclooctene rhodium chloride dimer ([RhCl (COE)
2]
2) preparation method of Cabbeen chelant complex of rhodium that formed of reaction.
Background technology
N-heterocycle carbine, as a kind of noticeable Novel Ligands, more and more causes extensive concern in metal organic coordination chemistry.Current N-heterocyclic carbene metal title complex has been successfully applied in homogeneous catalytic reaction, especially be widely used on C-C/C-N coupling reaction, hydrosilation reaction and olefin metathesis reaction, make it become rapidly the study hotspot of the scientific domain such as biological, chemical.
The N-heterocyclic carbene complexes of rhodium is as a member in transition metal carbene complexes extended family, be mainly used in catalyzed hydrosilation reaction, hydrosilation reaction is the reaction that in organic chemistry, a class is important, research finds that the arbine complex (NHC-Rh) of rhodium has good catalytic effect to this kind of reaction, and reaction conditions is gentle and can reach higher transformation efficiency.
(the Mata J A such as Mata, Chianese A R, Miecznikowski J R.et al.Reactivity differences in thesyntheses of chelating N-heterocyclic carbene complexes of rhodium are ascribed to ligandanisotropy.Organometallics, 2004, 23:1253-1263.) and (the Leung C H such as Leung, Incarvito C D, Crabtree R H.Interplay of Linker, N-substitutent, and counterion effects in the formation andgeometrical distortion of N-heterocyclic biscarbene complexes of rhodium (I) .Organometallics, 2006, N-heterocycle carbine non-chelated title complex and the chelant complex of Rh (I) 25:6099-6107.) has been synthesized with silver card guest Transmetallation.Above-mentioned research be after utilizing the Neo Heliopan AP of alkyl bridged linkage and silver suboxide to react again with cyclooctadiene rhodium chloride dimer ([RhCl (COD)]
2) react the arbine complex forming rhodium, only containing a bidentate carbenes in each complex molecule.Chen Wanzhi, Liu Bo (a kind of method of synthesis of azacyclic arbine complex, CN102351907A, 2012,02,15.) utilize nickel aza ring carbene complex to prepare the arbine complex of the rhodium of monokaryon as Cabbeen transfering reagent.Above substance catalyses active site is analyzed less, catalytic activity Shortcomings from structure.
Double-core rhodium arbine complex prepared by the present invention, different from the monokaryon rhodium arbine complex structure that patent CN102351907A invents.In order to prepare the arbine complex of the rhodium of novel structure thus improve its catalytic performance in hydrosilation reaction, the present invention is by bicyclooctene rhodium chloride dimer ([RhCl (COE)
2]
2) replace cyclooctadiene rhodium chloride dimer ([RhCl (COD)]
2), and intermediate product double-core silver carbene complex is separated, point two step method has prepared the rhodium arbine complex of the double-core of novel structure, containing two bidentate carbenes in each complex molecule, adds the catalytic activity point of title complex.
Technology contents
The advantage of the present invention compared with background technology there is provided a kind of preparation method of arbine complex of rhodium of novel structure, contains double-core and simultaneously containing two bidentate carbenes, the active site of its catalyzed chemical reaction is increased in each complex molecule.
Technical scheme of the present invention is:
An aza ring carbene complex for rhodium, its chemical formula is as follows:
Wherein, n=3 or 4.
The preparation method of the aza ring carbene complex of described rhodium, comprises the following steps:
1). the muriatic synthesis of bidentate N-heterocycle glyoxalidine: take THF as solvent, in sealed tube, add 1-Methylimidazole and dichloro-alkane, under sealing, be warming up to 170 ~ 190 DEG C, react after 36 ~ 48 hours, filter and also wash with THF, dry bidentate N-heterocycle glyoxalidine muriate.Every mmole 1-Methylimidazole needs solubilizing agent 0.5ml, and material proportion is mol ratio 1-Methylimidazole: dichloro-alkane=1:0.5 ~ 1;
2). the synthesis of double-core silver carbene complex: under anhydrous and oxygen-free and nitrogen protection; compare for the mixing solutions of 1:0.5 ~ 1 is for solvent with methyl alcohol and methylene chloride volume; bidentate N-heterocycle glyoxalidine muriate and silver suboxide that upper step obtains is added in schlenk reaction flask; stirring at room temperature reaction, after 10 ~ 12 hours, is filtered, is drained solvent, n-hexane, dry double-core silver carbene complex.Every mmole bidentate N-heterocycle glyoxalidine muriate need add mixed solvent 10ml, and material proportion is mol ratio bidentate N-heterocycle glyoxalidine muriate: silver suboxide=1:2 ~ 3;
3). the synthesis of the reacting precursor of rhodium: be that the mixing solutions of 1:3 ~ 4 is added in reaction flask with volume ratio by distilled water and Virahol; three water Trichlororhodium and cyclooctene are added again in reaction flask; ambient temperature under nitrogen protection sealing after 0.5 ~ 1 hour; stirring reaction 96 ~ 120 hours, filter and with ethanol wash, the reacting precursor of dry rhodium.Every mmole three water Trichlororhodium need add mixing solutions 5 ~ 7ml, and material proportion is mol ratio three water Trichlororhodium: cyclooctene=1:3 ~ 6;
4). the synthesis of the arbine complex of rhodium: under anhydrous and oxygen-free and nitrogen protection; take methyl alcohol as solvent; reacting precursor and the double-core silver carbene complex of rhodium is added in schlenk reaction flask; stirring at room temperature, after 8 ~ 12 hours, is filtered, is drained solvent, n-hexane, the dry arbine complex obtaining rhodium.Every mmole double-core silver carbene complex needs solubilizing agent 100 ~ 125ml methyl alcohol, and material proportion is the reacting precursor of mol ratio rhodium: double-core silver carbene complex=1:1 ~ 2.
Described dichloro-alkane is 1,3-propylene dichloride or Isosorbide-5-Nitrae-dichlorobutane;
Described bidentate N-heterocycle glyoxalidine muriate is 1,1 '-dimethyl-3,3 '-propylidene-two (glyoxalidine)-dichloride or 1,1 '-dimethyl-3,3 '-butylidene-two (glyoxalidine)-dichloride;
The present invention extends the structure diversity of the title complex of rhodium, and the title complex family for rhodium adds the member of novel structure.This title complex is a kind of good catalyzer, environmentally friendly, is with a wide range of applications in chemical industry.Present method reaction conditions is gentle, and aftertreatment is simple, productive rate higher (the best can reach 75%, as embodiment 2).The present invention is that the title complex that low cost is synthesized containing the double-core rhodium of bidentate carbenes provides simple approach.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of the double-core silver carbene complex of butylidene bridging in embodiment 2.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of the arbine complex of the rhodium of butylidene bridging in embodiment 2.
Fig. 3 is the nuclear-magnetism carbon spectrum spectrogram of the arbine complex of the rhodium of butylidene bridging in embodiment 2.
Embodiment
Embodiment 1
1, the synthesis of 1 '-dimethyl-3,3 '-propylidene-two (glyoxalidine)-dichloride: 20mmol1-Methylimidazole is put into a sealable test tube, add 10mlTHF and 11mmol1,3-propylene dichloride, sealing test tube, heating test tube to 175 DEG C, react and to be cooled to room temperature filtration after 40 hours and to wash with THF, vacuum-drying obtains pale powder: 1,1 '-dimethyl-3,3 '-propylidene-two (glyoxalidine)-dichloride, productive rate 81%.
1H NMR(400MHz，D
2O)：δ8.74(s，2H，NCHN)，7.44(d，4H，Him)，4.27(t，4H，NCH
2)，3.85(s，6H，CH
3)，2.47(m，2H，CH
2)。
The synthesis of the double-core silver carbene complex of propylidene bridging: under anhydrous and oxygen-free and nitrogen protection; by 2mmol1; 1 '-dimethyl-3; 3 ' ' schlenk reaction flask put into by-propylidene-two (glyoxalidine)-dichloride and 4mmol silver suboxide; add 10ml methylene dichloride and 10ml methyl alcohol; room temperature lucifuge stir after 10 hours leave standstill, upper strata is pale red brown liquid; lower floor is gray precipitate; collecting by filtration solution, vacuum drain solvent, n-hexane, vacuum-drying obtain red-brown powder: the double-core silver carbene complex of propylidene bridging, productive rate 60%.
1H NMR(400MHz，D
2O)：δ7.36(d，8H，Him)，4.15(t，8H，NCH
2)，3.54(s，12H，CH
3)，2.58(m，4H，CH
2)。
13C NMR(100MHz，D
2O)：δ181.5(Ag-C)，122.4，48.9，38.5，27.3。
The synthesis of the reacting precursor of rhodium: by 0.8mmol tri-water Trichlororhodium; 4ml Virahol; 1ml distilled water and 4.6mmol cyclooctene are placed in reaction flask; ambient temperature under nitrogen seals after protecting 0.5 hour; stirring reaction left standstill after 96 hours, filtration, washing with alcohol, vacuum-drying obtain yellow powder: the reacting precursor of rhodium, productive rate 70%.
1H NMR(400MHz，CDCl
3)：δ5.62(m，8H，CH)，2.14(m，16H，CHCH
2)，1.49(m，32H，CHCH
2CH
2)。
The synthesis of the arbine complex of the rhodium of propylidene bridging: under anhydrous and oxygen-free and nitrogen protection; the double-core silver carbene complex of 0.04mmol propylidene bridging and the reacting precursor of 0.04mmol rhodium are placed in schlenk reaction flask; add 5ml methyl alcohol; stirring at room temperature left standstill after 10 hours; upper strata is pale red brown liquid; lower floor is a small amount of grey powder; collecting by filtration solution, vacuum drain solvent, n-hexane, vacuum-drying obtain brown ceramic powder: the arbine complex of the rhodium of propylidene bridging, productive rate is 68%.
1H NMR(400MHz，D
2O)：δ7.29(d，8H，Him)，4.07(t，8H，NCH
2)，3.73(s，12H，CH
3)，1.73(m，4H，CH
2)。
13c NMR (100MHz, CD
3oD): δ 183.1 (Rh-C), 123.7,49.1,36.4,28.1, corresponding to the n=3 in the arbine complex chemical formula of rhodium in technical scheme.
Embodiment 2
1, the synthesis of 1 '-dimethyl-3,3 '-butylidene-two (glyoxalidine)-dichloride: 20mmol1-Methylimidazole is put into a sealable test tube, add 10mlTHF and 15mmol1,4-dichlorobutane, sealing test tube, heating test tube to 185 DEG C, react and to be cooled to room temperature filtration after 48 hours and to wash with THF, vacuum-drying obtains pale powder: 1,1 '-dimethyl-3,3 '-butylidene-two (glyoxalidine)-dichloride, productive rate 87%.
1H NMR(400MHz，D
2O)：δ8.67(s，2H，NCHN)，7.39(d，4H，Him)，4.18(t，4H，NCH
2)，3.83(s，6H，CH
3)，1.84(m，4H，CH
2)。
The synthesis of the double-core silver carbene complex of butylidene bridging: under anhydrous and oxygen-free and nitrogen protection; by 2mmol1; 1 '-dimethyl-3; schlenk reaction flask put into by 3 '-butylidene-two (glyoxalidine)-dichloride and 4.8mmol silver suboxide; add 10ml methylene dichloride and 10ml methyl alcohol; room temperature lucifuge stir after 12 hours leave standstill, upper strata is reddish-brown liquid; lower floor is gray precipitate; collecting by filtration solution, vacuum drain solvent, n-hexane, vacuum-drying obtain red-brown powder: butylidene bridged binuclear silver carbene complex, productive rate 65%.
1H NMR(400MHz，CDCl
3)：δ7.31(d，4H，Him)，7.02(d，4H，Him)，4.34(t，8H，NCH
2)，3.89(s，12H，CH
3)，1.97(m，8H，CH
2)。
13C NMR(100MHz，CDCl
3)：δ181.7(Ag-C)，122.2，51.0，38.9，28.0。
The synthesis of the reacting precursor of rhodium: by 1.54mmol tri-water Trichlororhodium; 7ml Virahol; 2ml distilled water and 8.8mmol cyclooctene are placed in reaction flask; ambient temperature under nitrogen seals after protecting 1 hour; stirring reaction left standstill after 120 hours, filtration, washing with alcohol, vacuum-drying obtain yellow powder: the reacting precursor of rhodium, productive rate 73%.
1H NMR(400MHz，CDCl
3)：δ5.62(m，8H，CH)，2.14(m，16H，CHCH
2)，1.49(m，32H，CHCH
2CH
2)。
The synthesis of the arbine complex of the rhodium of butylidene bridging: under anhydrous and oxygen-free and nitrogen protection; the double-core silver carbene complex of 0.08mmol butylidene bridging and the reacting precursor of 0.05mmol rhodium are placed in schlenk reaction flask; add 8ml methyl alcohol; stirred at ambient temperature left standstill after 12 hours; upper strata is reddish-brown liquid; lower floor is a small amount of grey powder; collecting by filtration solution, vacuum drain solvent, n-hexane, vacuum-drying obtain brown ceramic powder: the arbine complex of the rhodium of butylidene bridging, productive rate is 75%.
1H NMR(400MHz，D
2O)：δ7.30(d，8H，Him)，4.08(t，8H，NCH
2)，3.75(s，12H，CH
3)，1.75(m，8H，CH
2)。
13c NMR (100MHz, CD
3oD): δ 183.6 (Rh-C), 125.1,50.4,36.6,27.2, corresponding to the n=4 in the arbine complex chemical formula of rhodium in technical scheme.
Not there is fignal center between δ 8-9ppm in the proton nmr spectra of this title complex, and on its carbon-13 nmr spectra, near δ 183.4ppm, occur a characteristic peak.The appearance at these characteristic signal peaks, describes the generation of the rhodium arbine complex obtaining chemical formula in previous technique scheme.
Described chemical reagent is commercially available acquisition.
Unaccomplished matter of the present invention is known technology.
Claims (2)
1. an aza ring carbene complex for rhodium, the chemical formula that it is characterized by this material is as follows:
Wherein, n=3 or 4.
2. the preparation method of the aza ring carbene complex of rhodium as claimed in claim 1, is characterized by and comprise the following steps:
1). the muriatic synthesis of bidentate N-heterocycle glyoxalidine: take THF as solvent, in sealed tube, add 1-Methylimidazole and dichloro-alkane, under sealing, be warming up to 170 ~ 190 DEG C, react after 36 ~ 48 hours, filter and also wash with THF, dry bidentate N-heterocycle glyoxalidine muriate; Every mmole 1-Methylimidazole needs solubilizing agent 0.5ml, and material proportion is mol ratio 1-Methylimidazole: dichloro-alkane=1:0.5 ~ 1;
2). the synthesis of double-core silver carbene complex: under anhydrous and oxygen-free and nitrogen protection, compare for the mixing solutions of 1:0.5 ~ 1 is for solvent with methyl alcohol and methylene chloride volume, in schlenk reaction flask, add bidentate N-heterocycle glyoxalidine muriate and silver suboxide that upper step obtains, stirring at room temperature reaction after 10 ~ 12 hours, filter, drain solvent, n-hexane, dry double-core silver carbene complex; Every mmole bidentate N-heterocycle glyoxalidine muriate need add mixed solvent 10ml, and material proportion is mol ratio bidentate N-heterocycle glyoxalidine muriate: silver suboxide=1:2 ~ 3;
3). the synthesis of the reacting precursor of rhodium: be that the mixing solutions of 1:3 ~ 4 is added in reaction flask with volume ratio by distilled water and Virahol, three water Trichlororhodium and cyclooctene are added again in reaction flask, ambient temperature under nitrogen protection sealing after 0.5 ~ 1 hour, stirring reaction 96 ~ 120 hours, filter and with ethanol wash, the reacting precursor of dry rhodium; Every mmole three water Trichlororhodium need add mixing solutions 5 ~ 7ml, and material proportion is mol ratio three water Trichlororhodium: cyclooctene=1:3 ~ 6;
4). the synthesis of the arbine complex of rhodium: under anhydrous and oxygen-free and nitrogen protection, take methyl alcohol as solvent, in schlenk reaction flask, add reacting precursor and the double-core silver carbene complex of rhodium, stirring at room temperature after 8 ~ 12 hours, filter, drain the arbine complex of solvent, n-hexane, dry rhodium; Every mmole double-core silver carbene complex needs solubilizing agent 100 ~ 125ml methyl alcohol, and material proportion is the reacting precursor of mol ratio rhodium: double-core silver carbene complex=1:1 ~ 2.
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| C-H Oxidative Addition of Bisimidazolium Salts to Iridium and Rhodium Complexes, and N-Heterocyclic Carbene Generation. A Combined Experimental and Theoretical Study;Monica Viciano et al.;《Organometallics》;20060204;第25卷(第5期);第1120-1134页 * |
| Synthesis and Reactivity of a Platinum(II) Complex with Hydrosulfido Ligands Induced by a Chelated N-Heterocyclic Carbene Ligand;Yuri Maeda et al.;《Chemical Letter》;20120128;第41卷;第146页图1 * |
| 双N-杂环卡宾螯合配合物研究进展;承勇等;《化学研究与应用》;20120331;第24卷(第3期);346页第2节标题，第348页第3节标题，第345页图2，348页图9，第3346页图3和4 * |
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