CN101348501B - 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof - Google Patents

2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof Download PDF

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CN101348501B
CN101348501B CN200710119128XA CN200710119128A CN101348501B CN 101348501 B CN101348501 B CN 101348501B CN 200710119128X A CN200710119128X A CN 200710119128XA CN 200710119128 A CN200710119128 A CN 200710119128A CN 101348501 B CN101348501 B CN 101348501B
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phenyl
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phenanthroline
toluene
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CN101348501A (en
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孙文华
介素云
张树
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Institute of Chemistry CAS
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Abstract

The invention discloses a 2-imdo group-9-phenyl group-1, 10-phenanthrolines transition metal complex and a preparation method thereof and an application thereof. The structural formula of the 2-imdo group-9-phenyl group-1, 10-phenanthrolines transition metal complex of the invention is shown as the formula(I), wherein M is transition metal, and R and R<1> are independently selected from hydrogen,alkyl and phenyl respectively. In the invention, the ligand and the transition metal complex of 2-imdo group-9-phenyl group-1, 10-phenanthrolines containing N^N^N ligand are designed and synthesized;when the transition metal complex is used to catalyze the ethylene oligomerization reaction, the transition metal complex performs good catalytic activity and high selectivity of 1-butylene, so that the transition metal complex has broad industrial application prospect.

Description

2-imido grpup-9-phenyl-1,10-phenanthroline transient metal complex and preparation method thereof and application
Technical field
The present invention relates to a kind of 2-imido grpup-9-phenyl-1,10-phenanthroline transient metal complex and preparation method thereof, and catalyst composition of forming by this transition metal complex and the application of this catalyst composition in the catalyzed ethylene oligomerisation reaction.
Background technology
Linear alpha-alkene is very important organic chemical industry's intermediate, has different performances and purposes according to the length of its carbochain.C 4～C 8It is the comonomer of production of linear new LDPE (film grade) (LLDPE); C 8～C 12Can be as the basic material of producing senior lubricant; C 10～C 18It is the important source material of producing tensio-active agent, washing composition and clean-out system; High carbon number alpha-olefin is widely used in oilfield chemistry and paper setting agent etc.Present industrial production of linear alpha-olefins mainly is to adopt the method for ethylene oligomerization to realize.In recent years, countries in the world are increasing year by year to the demand of alpha-olefin, have data to show that the demand of world's alpha-olefin in 2002 reaches 3,400,000 tons, has kept the scale of world demand increment 4.9%; The market of alpha-olefin is considered to the central factor of the U.S. and West Europe economic growth, and this huge market is consuming full cut alpha-olefin, as: in West Europe, the senior lubricant of transportation means is the polymkeric substance of alpha-olefin; Family expenses still be industrial cleaning agent all be ethoxy compound, ether sulfuric ester of alpha-olefin etc.; And high-carbon alpha-olefin is widely used in oilfield chemistry and paper setting agent.Since the seventies, the research of transition metal complex homogeneous catalysis ethylene oligomerization is subject to people's attention, shell (Shell) company has found shell higher olefins preparation technology the earliest, it is SHOP (Shell HigherOlefin Process) technological process, relevant patent: US Patent3686351,19720711 and US Pantent3676523,19720822, this is O-P bridging type coordination nickel catalyzator (formula A), and the ethylene oligomerization catalysis activity is approximately 10 5Gmol -1(Ni) h -1, 99% is linear alpha-olefins in this technology products therefrom, wherein alpha-olefin accounts for 98%, and suitability for industrialized production and widespread use.
Figure S071B9128X20070813D000011
(formula A)
People also make great efforts to study new catalyst when improving existing catalyzer, simplify the synthetic and preparation technology of catalyzer, improve the catalytic activity of catalyzer and the selectivity of catalysate.Having developed multiple in recent years again is the post-transition metal catalyst system of dentate with heteroatomss such as O, N, P, wherein the nitrogen-atoms catalyzer of making the coordination tooth is subjected to people's extensive attention, as recent patent: Jpn.Kokai Tokkyo Koho JP 11060627, A22 Mar 1999Heisei; PCTInt.Appl.WO9923096A114May1999; PCTInt.Appl.WO9951550A114 Oct 1999.
Ethylene oligomerization is observed identical reaction mechanism with polymerization, thereby ethylene oligomerization and polymerization are the products of two class different in kinds of catalyzed ethylene reaction.Half of macromolecular material usage quantity is polyolefin resin, olefin resin is compared with other resin material has fine environment Harmony, be used to the material that emphasis is promoted in developed country's automobile industry, the world production amount in 2003 has just reached 8,330 ten thousand tons; Wherein polyethylene is a synthetic resins with fastest developing speed, that output is maximum, purposes is extremely wide, reaches 5,110 ten thousand tons then.Industrialized polyethylene catalysts has Ziegler-Natta type catalyzer (DE Pat889229 (1953); IT Pat545332 (1956) and IT Pat536899 (1955); Chem.Rev., 2000,100,1169 and this special issue pertinent literature), Phillips type catalyzer (Belg.Pat.530617 (1955); Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky, Metalorganic Catalysts for Synthesis andPolymerization, Berlin:Springer, 1999), and the efficient ethylene oligomerization and the polymerizing catalyst of the rear transition metal metal compounding material type of development in recent years.Nineteen ninety-five, Brookhart etc. have reported the title complex of a class alpha-diimine Ni (II), can high reactivity ground polymerising ethylene, its structure be shown below (J.Am.Chem.Soc., 1995,117,6414-6415):
Figure S071B9128X20070813D000021
1998, Brookhart and Gibson etc. reported the title complex of pyridine diimine iron (II) and cobalt (II) again simultaneously, by regulating the substituting group on the phenyl ring, oligomerisation or polymerising ethylene well, its structure is suc as formula (J.Am.Chem.Soc., 1998 shown in the B, 120,4049-4050; Chem.Commun.1998,849-850):
(formula B)
At present, industrial main employing Ni, Cr, Zr and Z-N Catalyst Production alpha-olefin mainly concentrate on three major companies, are respectively BP, Chevron Phillips and Shell, and all there are independently production technique and technology in several companies.The oligomerization process of shell (Shell) company mainly is synthetic high carbon chain alpha-olefin, is used for sanitising agent and washing composition intermediate, and the ethylene oligomerization catalysis activity is approximately 10 5Gmol -1(Ni) h -1, 99% is linear alpha-olefins in the products therefrom, wherein alpha-olefin accounts for 98%.Because this process using high pressure oligomerisation, equipment cost and operation cost are all higher, and the target of development still is the low pressure oligomerisation at present.Nickel catalyst needs high pressure catalysis technique and technology, and has the potentially dangerous of double-bond shift generation internal olefin, operational condition harshness; Other a few class catalyzer all are to transform on the polyolefin catalyst basis and modification forms producing, and often careless manipulation can cause high polyolefine to generate, and stops up discharge port.Therefore, the novel high reactivity ethylene oligomerization catalyst of research and development is the key point of the new ethylene oligomerization technology of exploitation.
Summary of the invention
The purpose of this invention is to provide a kind of 2-imido grpup-9-phenyl-1,10-phenanthroline transient metal complex and preparation method thereof.
2-imido grpup of the present invention-9-phenyl-1,10-phenanthroline transient metal complex, structural formula be suc as formula shown in the I,
Figure S071B9128X20070813D000031
Wherein, M is a transition metal;
R and R 1Be selected from hydrogen, alkyl and phenyl independently of one another.
Preferably, M is Fe, Co or Ni; R 1Be selected from hydrogen, methyl, ethyl, sec.-propyl; R is selected from methyl and phenyl.Preferred, metal complexes of the present invention is selected from following any one title complex:
M＝Fe，R＝Me，R 1＝Me； M＝Fe，R＝Me，R 1＝Et；
M＝Fe，R＝Me，R 1＝iPr； M＝Fe，R＝Ph，R 1＝Me；
M＝Fe，R＝Ph，R 1＝Et； M＝Fe，R＝Ph，R 1＝iPr；
M＝Co，R＝Me，R 1＝Me； M＝Co，R＝Me，R 1＝Et；
M＝Co，R＝Me，R 1＝iPr； M＝Co，R＝Ph，R 1＝Me；
M＝Co，R＝Ph，R 1＝Et； M＝Co，R＝Ph，R 1＝iPr；
M＝Ni，R＝Me，R 1＝Me； M＝Ni，R＝Me，R 1＝Et；
M＝Ni，R＝Me，R 1＝iPr； M＝Ni，R＝Ph，R 1＝Me；
M＝Ni，R＝Ph，R 1＝Et； M＝Ni，R＝Ph，R 1＝iPr；
Here, the Me represent methylidene, Et represents ethyl, and iPr represents sec.-propyl, and Ph represents phenyl.
The preparation method of this transition metal complex comprises the steps:
1) with 2-ethanoyl-9-phenyl-1,10-phenanthroline or 2-benzoyl-9-phenyl-1, aniline reaction Synthetic 2-imido grpup-9-phenyl-1 that 10-phenanthroline and alkyl replace, 10-phenanthroline part;
2) with the 2-imido grpup-9-phenyl-1 that obtains in the step 1), 10-phenanthroline part and transition metal reactant salt can obtain described title complex.
Wherein, the step 1) reaction is a catalyzer with the tosic acid.
Another object of the present invention provides the purposes of metal complexes of the present invention.
Metal complexes of the present invention can be formed a kind of catalyst composition that is used for ethylene oligomerization.
This catalyst composition comprises Primary Catalysts and promotor, and wherein, Primary Catalysts is 2-imido grpup of the present invention-9-phenyl-1, and 10-phenanthroline transient metal complex, promotor are selected from aikyiaiurnirsoxan beta, alkylaluminium cpd and chlorination aluminum alkyls.
Preferably, aikyiaiurnirsoxan beta is the methylaluminoxane of methylaluminoxane, modification; Aluminum alkyls and chlorination aluminum alkyls comprise trimethyl aluminium, triethyl aluminum, diethylaluminum chloride, ethylaluminium dichloride.The mol ratio of metallic aluminium and Primary Catalysts central metal Al/M is 100 to 2000 in the promotor.
In catalyst composition, can also add the assistant ligand triphenylphosphine, can improve catalytic activity and prolong life of catalyst, the mol ratio of triphenylphosphine and Primary Catalysts is 50-1:1.
The application of above-mentioned catalyst composition in the catalyzed ethylene oligomerisation reaction also belongs to protection scope of the present invention.Preferably, the temperature of oligomerisation reaction is 20 to 80 ℃, and ethylene pressure is 10-0.1MPa.
The present invention has designed and synthesized the 2-imido grpup-9-phenyl-1 that contains the N^N^N dentate, 10-phenanthroline part and transition metal complex, this metal complexes is used for the catalyzed ethylene oligomerisation reaction, show excellent catalytic activity and high 1-butylene selectivity, have the wide industrial application prospect.
Description of drawings
Fig. 1 is the crystalline structure figure of part 2;
Fig. 2 is the crystalline structure figure of title complex 2;
Fig. 3 is the crystalline structure figure of title complex 7;
Fig. 4 is the crystalline structure figure of title complex 10;
Fig. 5 is the crystalline structure figure of title complex 12;
Fig. 6 is the crystalline structure figure of title complex 13;
Fig. 7 is the crystalline structure figure of title complex 17.
Embodiment
Title complex of the present invention can synthesize according to following equation:
Figure S071B9128X20070813D000051
Concrete steps are as follows:
1, with 2-ethanoyl-9-phenyl-1,10-phenanthroline or 2-benzoyl-9-phenyl-1, the aniline reaction Synthetic 2-imido grpup of 10-phenanthroline and replacement-9-phenyl-1,10-phenanthroline part;
2, with 2-imido grpup-9-phenyl-1,10-phenanthroline part respectively with transition metal salt (as FeCl 24H 2O, CoCl 2, NiCl 26H 2O etc.) reaction can obtain title complex.
Wherein, 2-ethanoyl-9-phenyl-1; the main synthesis step of 10-phenanthroline is: (1) 2-ethanoyl-1; 10-phenanthroline, ethylene glycol and tosic acid reflux in toluene (100mL) did not have water to generate in 18 hours in water-and-oil separator; remove residuum parlkaline aluminum oxide pillar purifying behind the solvent toluene; with petrol ether/ethyl acetate (1:2) drip washing, second flow point is a condensation product.(2) the phenyl lithium drips of solution is added in the toluene suspension of products therefrom in the step (1), yellow originally becomes brown.After dropwising, reaction soln continued stirring reaction 3 hours under 0 ℃ and nitrogen protection.Then, carefully add entry and stir stopped reaction, the xanchromatic organic layer separates, and water layer merges organic phase subsequently and uses anhydrous sodium sulfate drying with dichloromethane extraction several times.Concentrate organic layer, residuum is crossed silica gel pillar purifying and is obtained yellow oil.Above-mentioned gained yellow oil is dissolved in acetone, and adds tosic acid and make catalyzer, reflux 15 hours, product is precipitated out from solution, obtains light yellow solid product 2-ethanoyl-9-phenyl-1 after the filtration, the 10-phenanthroline.
2-benzoyl-9-phenyl-1, the main synthesis step of 10-phenanthroline is: under-78 ℃ and nitrogen protection, the phenyl lithium drips of solution is added to 2-cyano group-1, in the toluene suspension of 10-phenanthroline, slowly rises to room temperature after dropwising and stir and spend the night.Reaction is ended by slowly adding water, and red organic layer separates, and water layer merges organic phase subsequently and uses anhydrous sodium sulfate drying with dichloromethane extraction several times.Concentrate organic layer, residuum is crossed silica gel pillar purifying and is obtained yellow solid product 2-benzoyl-9-phenyl-1,10-phenanthroline.
Preferably, can obtain the title complex of following replacement situation:
1：M＝Fe，R＝Me，R 1＝Me； 2：M＝Fe，R＝Me，R 1＝Et；
3：M＝Fe，R＝Me，R 1＝iPr； 4：M＝Fe，R＝Ph，R 1＝Me；
5：M＝Fe，R＝Ph，R 1＝Et； 6：M＝Fe，R＝Ph，R 1＝iPr；
7：M＝Co，R＝Me，R 1＝Me； 8：M＝Co，R＝Me，R 1＝Et；
9：M＝Co，R＝Me，R 1＝iPr； 10：M＝Co，R＝Ph，R 1＝Me；
11：M＝Co，R＝Ph，R 1＝Et； 12：M＝Co，R＝Ph，R 1＝iPr；
13：M＝Ni，R＝Me，R 1＝Me； 14：M＝Ni，R＝Me，R 1＝Et；
15：M＝Ni，R＝Me，R 1＝iPr； 16：M＝Ni，R＝Ph，R 1＝Me；
17：M＝Ni，R＝Ph，R 1＝Et； 18：M＝Ni，R＝Ph，R 1＝iPr；
Concrete preparation process is as follows:
One. part synthetic general method
1.2-ethanoyl-9-phenyl-1; the aniline that 10-phenanthroline and alkyl replace is that catalyzer refluxed 1 day with the tosic acid in toluene; reaction solution concentrates back parlkaline aluminum oxide pillar; with petrol ether/ethyl acetate (20:1) drip washing; second flow point is a product; removing desolvates obtains yellow solid, is respective ligand.
2.2-benzoyl-9-phenyl-1; the aniline that 10-phenanthroline and alkyl replace is catalyzer with the tosic acid; adopt tetraethoxy to make solvent and dewatering agent; 140-150 ℃ of following reacting by heating 1.5 days, tetraethoxy, parlkaline aluminum oxide pillar were then removed in decompression; with petrol ether/ethyl acetate (6:1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid, is respective ligand.
Above-mentioned all synthetic 2-imido grpup-9-phenyl-1,10-phenanthroline part have all obtained confirmation by nuclear-magnetism, infrared and ultimate analysis.
Two. iron (II), cobalt (II), nickel (II) title complex synthetic general method
With FeCl 24H 2O, CoCl 2Or NiCl 26H 2O and 2-imido grpup-9-phenyl-1,10-phenanthroline part (1:1) in molar ratio mix, and add tetrahydrofuran (THF) or ethanol and make solvent, at room temperature stirred 9 hours, separate out precipitation, filter with ether washing after drying and just obtain 2-imido grpup-9-phenyl-1,10-phenanthroline title complex.
Use title complex of the present invention and can also form a kind of ethylene oligomerization catalyst for reaction composition that is used for, it comprises Primary Catalysts and is used for Primary Catalysts activatory promotor (being activator).Described Primary Catalysts is 2-imido grpup of the present invention-9-phenyl-1,10-phenanthroline title complex, and aikyiaiurnirsoxan beta, alkylaluminium cpd and chlorination aluminum alkyls etc. can use as promotor.The example of aikyiaiurnirsoxan beta comprises methylaluminoxane (MMAO), ethyl aikyiaiurnirsoxan beta and the isobutyl aluminium alkoxide of methylaluminoxane (MAO), triisobutyl aluminium modification.Aikyiaiurnirsoxan beta can produce by the hydrolytic action of various trialkyl aluminium compounds, and MMAO can produce by the hydrolytic action of trimethyl aluminium and more senior trialkylaluminium such as triisobutyl aluminium; The example of alkylaluminium cpd and chlorination aluminum alkyls comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride, ethylaluminium dichloride etc.Preferably, select aikyiaiurnirsoxan beta alkane and chlorination aluminum alkyls for use, as the methylaluminoxane (MMAO) of methylaluminoxane (MAO), triisobutyl aluminium modification and diethylaluminum chloride as promotor.
For above-mentioned catalyst composition, under the synergy of the methylaluminoxane (being abbreviated as MMAO) of promotor methylaluminoxane (being abbreviated as MAO) or triisobutyl aluminium modification, the oligomerisation activity that iron (II) title complex shows ethene, product mainly is a butylene, and to the selectivity of 1-butylene up to more than 99%; Under the synergy of promotor methylaluminoxane (being abbreviated as MAO), cobalt (II) title complex shows higher activity to ethylene oligomerization, and the oligopolymer of generation is mainly butylene, hexene, octene etc., and also reaches more than 95% to the selectivity of 1-butylene; At promotor diethyl aluminum chloride (Et 2AlCl) under the synergy, nickel (II) title complex shows medium oligomerisation activity to ethene, yet the adding of assistant ligand triphenylphosphine can improve the catalytic activity of nickel complex greatly and prolong life of catalyst.
Below title complex of the present invention is described and for the catalytic process of ethylene oligomerization reaction with specific embodiment.
Embodiment 1
1.2-ethanoyl-9-phenyl-1, the preparation of 10-phenanthroline:
1) 2-ethanoyl-1; 10-phenanthroline (2.823g; 10.0mmol), ethylene glycol (3.254g; 52.4mmol) and tosic acid (206mg) in toluene (100mL), reflux and in water-and-oil separator, do not have water to generate in 18 hours; remove residuum parlkaline aluminum oxide pillar purifying behind the solvent toluene, with petrol ether/ethyl acetate (1:2) drip washing, second flow point is a product; obtain light yellow solid 1.691g after concentrating, productive rate is 50%.Fusing point is 119-121 ℃.
FT-IR(KBr?disc)：3054，2993，2980，2938，2900，1619，1589，1552，1505，1490，1476，1445，1391，1376，1256，1232，1204，1147，1129，1106，1029，1009，953，855，789，752，675cm-1。
1H?NMR(400MHz，CDCl3)：δ＝9.24(d，J＝4.4Hz，1H)，8.25(d，J＝8.4Hz，1H)，8.22(d，J＝8.4Hz，1H)，7.93(d，J＝8.4Hz，1H)，7.77(s，2H)，7.61(dd，J＝4.4Hz，1H)，4.18(t，J＝6.4Hz，2H)，4.01(t，J＝6.4Hz，2H)，1.98(s，3H)。
13C?NMR(100MHz，CDCl3)：δ＝161.5，150.5，146.4，145.8，136.8，136.0，129.0，128.1，126.7，126.3，122.9，119.5，65.2，25.6。
Ultimate analysis (C 16H 14N 2O 2) theoretical value (%): C72.16, H5.30, N10.52; Experimental value (%): C72.18, H5.23, N11.00.
2) (0.9mL, diethyl ether solution 8.5mmol) (20mL) are added drop-wise to 2 normal metallic lithiums, and (118mg 17.0mmol) makes phenyl lithium solution in the ether suspension (30mL) to bromobenzene under room temperature and nitrogen protection.Under 0 ℃ and nitrogen protection, the phenyl lithium drips of solution that makes is added to products therefrom in the step 1), and (1.333g, in toluene suspension 5.0mmol) (40mL), yellow originally becomes brown.After dropwising, reaction soln continued stirring reaction 3 hours under 0 ℃ and nitrogen protection.Then, carefully add entry (100mL) and stir stopped reaction, the xanchromatic organic layer separates, and water layer merges organic phase subsequently and uses anhydrous sodium sulfate drying with dichloromethane extraction several times.Concentrate organic layer, residuum is crossed silica gel pillar purifying and is obtained yellow oil.Above-mentioned gained yellow oil is dissolved in acetone (50mL), and adding tosic acid (170mg) is made catalyzer, reflux 15 hours; product is precipitated out from solution; obtain light yellow solid product 2-ethanoyl-9-phenyl-1 after the filtration, 10-phenanthroline 0.710g, productive rate are 47.5%.Fusing point is 184-186 ℃.
FT-IR(KBr?disc)：3103，3026，2916，1694，1633，1620，1597，1565，1537，1495，1367，1285，1219，1190，1120，1034，1011，888，817，766，741，678，566cm-1。
1H?NMR(300MHz，CDCl3)：δ＝8.44(d，J＝7.2Hz，2H)，8.34(d，J＝3.0Hz，2H)，8.30(d，J＝8.4Hz，1H)，8.17(d，J＝8.4Hz，1H)，7.88(d，J＝8.7Hz，1H)，7.78(d，J＝8.7Hz，1H)，7.59(t，J＝7.2Hz，2H)，7.50(t，J＝7.2Hz，1H)，3.14(s，3H)。
13C?NMR(75MHz，CDCl3)：δ＝200.3，156.6，152.3，145.4，144.8，138.5，136.5，130.4，129.3，128.4，128.1，127.3，127.0，125.3，119.7，119.6，25.2。
Ultimate analysis (C 20H 14N 2O) theoretical value (%): C80.52, H4.73, N9.39; Experimental value (%): C80.00, H4.77, N9.36.
2.2-ethanoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-xylidine) preparation of part [ligand 1]: 2-ethanoyl-9-phenyl-1; 10-phenanthroline (0.225g; 0.75mmol) and 2; 6-xylidine (0.184g; 1.5mmol) add the 80mg tosic acid and make catalyzer; under the nitrogen protection 20ml reflux in toluene 1 day; concentrate back residuum parlkaline aluminum oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.104g, and productive rate is 34.6%.Fusing point is 190-192 ℃.
FT-IR(KBr?disc)：3041，3018，2914，1635，1605，1590，1546，1506，1485，1467，1362，1293，1204，1118，1091，855，761，739，687cm -1。
1H?NMR(300MHz，CDCl 3)：δ8.80(d，J＝8.4Hz，1H)；8.45(d，J＝7.8Hz，2H)；8.34(d，J＝8.7Hz，2H)；8.18(d，J＝8.4Hz，1H)；7.85(d，J＝3.9Hz，2H)；7.56(t，J＝7.5Hz，2H)；7.47(t，J＝7.2Hz，1H)；7.11(d，J＝7.5Hz，2H)；6.97(t，J＝7.5Hz，1H)；2.62(s，3H)；2.09(s，6H)。
13C?NMR(75MHz，CDCl 3)：δ168.0，156.9，155.8，149.0，146.0，145.1，139.2，137.1，136.5，129.8，129.6，128.9，127.9，127.8，127.5，127.3，126.1，125.3，123.1，120.6，119.9，18.0，16.7。
Ultimate analysis (C 28H 23N 3) theoretical value (%): C83.76, H5.77, N10.47; Experimental value (%): C83.69, H5.76, N10.40.
3. the preparation that iron (II) [title complex 1] closed in chlorination [2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-xylidine)]: with 2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-xylidine) part (0.0806g, 0.2mmol) and FeCl 24H 2O (0.040g 0.2mmol) places the Schlenk pipe, behind the vacuum nitrogen filling gas three times, adds the tetrahydrofuran (THF) of the 4ml degassing, and reaction solution is earlier by the very fast generation green precipitate of green solution, and stirring reaction is 9 hours under the room temperature, the gained sedimentation and filtration, and filtrate be green; Precipitation is with ether washing, dry shallow green powder 0.1043g, and productive rate is 98.4%.
FT-IR(KBr?disc)：3059，2953，2918，2867，1615，1590，1555，1504，1491，1468，1451，1435，1374，1299，1205，865，792，772，745，702cm -1。
Ultimate analysis (C 28H 23Cl 2FeN 31/2CH 2Cl 2): C59.98, H4.24, N7.36; Experimental value (%): C59.61, H4.34, N7.28.
4. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) title complex 1 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500 (mol ratio, down together).Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.Reaction finishes the back and takes out spiece with 5% dilute hydrochloric acid neutralization carrying out GC analysis with syringe: the oligomerisation activity is 2.59 * 10 3Gmol -1(Fe) h -1, the oligopolymer of generation has only butylene, and wherein 1-butylene content is 96.1%.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 2
1. the preparation of title complex 1 is with embodiment 1.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) title complex 1 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the methylaluminoxane (MMAO) (n-heptane solution of 1.93mol/l) of 1.3ml modification again, make Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.Reaction finishes the back and takes out spiece with 5% dilute hydrochloric acid neutralization carrying out GC analysis with syringe: the oligomerisation activity is 4.78 * 10 5Gmol -1(Fe) h -1, the oligopolymer of generation has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 3
1. the preparation of title complex 1 is with embodiment 1.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 1 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.08 * 10 5Gmol (Fe) -1H -1, oligomer content is respectively: C 499.2%, C 60.8%, be 99.8% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 4
1. the preparation of title complex 1 is with embodiment 1.
2. (1MPa) ethylene oligomerization pressurizes: with the methylaluminoxane (MMAO) of 50ml toluene, the modification of 1.3ml triisobutyl aluminium, 1.93mol/l n-heptane solution), the toluene solution and the toluene of 20ml title complex 1 (5.0 μ mol) joins in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.69 * 10 6Gmol -1(Fe) h -1, oligomer content is respectively: C 499.4%, C 60.6%, the butylene of generation all is a 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 5
1.2-ethanoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) preparation of part [part 2]: 2-ethanoyl-9-phenyl-1; 10-phenanthroline (0.446g; 1.5mol); 2; 6-Diethyl Aniline (0.4906g; 3.2mmol) and the 118mg tosic acid in 20ml toluene, heating reflux reaction 8 hours, raw material reaction is complete; revolve to steam and remove toluene; residuum supports with methylene dichloride dissolving back neutral alumina, crosses the neutral alumina pillar, with petrol ether/ethyl acetate (6:1) drip washing; with obtaining orange solids 0.284g after the ether washing drying, productive rate is 44.2% behind the evaporate to dryness.Fusing point is 181-183 ℃.
FT-IR(KBr?disc)：3060，3037，2960，2929，2868，1639，1608，1589，1546，1507，1486，1452，1418，1369，1296，1258，1194，1119，1099，862，828，762，740，686cm -1。
1H?NMR(300MHz，CDCl 3)：δ8.80(d，J＝8.4Hz，1H)；8.45(d，J＝7.5Hz，2H)；8.33(d，J＝8.4Hz，2H)；8.17(d，J＝8.4Hz，1H)；7.80(d，J＝3.9Hz，2H)；7.56(t，J＝7.5Hz，2H)；7.47(t，J＝6.9Hz，1H)；7.16(d，J＝7.2Hz，2H)；7.07(t，J＝7.2Hz，1H)；2.64(s，3H)；2.42(q，J＝7.2Hz，4H)；1.16(t，J＝7.2Hz，6H)。
13C?NMR(75MHz，CDCl 3)：δ167.7，156.9，155.9，148.0，146.0，145.1，139.2，137.1，136.5，131.1，129.8，129.6，128.9，127.8，127.5，127.3，126.1，126.0，123.4，120.5，119.8，24.7，17.0，13.8。
Ultimate analysis (C 30H 27N 3) theoretical value (%): C83.88, H6.34, N9.78; Experimental value (%): C83.66, H6.40, N9.60.
Its crystalline structure as shown in Figure 1.
2. the preparation that iron (II) [title complex 2] closed in chlorination [2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-Diethyl Aniline)]: with 2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-Diethyl Aniline) part (0.0864g, 0.2mmol) and FeCl 24H 2(0.0401g 0.2mmol) places the Schlenk pipe to O, behind the vacuum nitrogen filling gas three times, the tetrahydrofuran (THF) that adds the 4ml degassing, reaction solution is earlier by the very fast generation green precipitate of green solution, and stirring reaction is 9 hours under the room temperature, gained sedimentation and filtration, filtrate are pale brown look; Precipitation is with ether washing, dry dusty blue powder 0.1073g, and productive rate is 95.9%.
FT-IR(KBr?disc)：3063，2966，2929，2872，1617，1584，1558，1504，1490，1442，1374，1289，1243，1205，1193，1152，1141，1060，859，786，759，744，701cm -1。
Ultimate analysis (C 30H 27Cl 2FeN 3) theoretical value (%): C64.77, H4.89, N7.55; Experimental value (%): C64.26, H4.59, N7.50.
Its crystalline structure as shown in Figure 2.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.8mg (5 μ mol) title complex 2 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out GC and analyze: the active 590g.mol of being of oligomerisation -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 6
1. the preparation of title complex 2 is with embodiment 5.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.8mg (5 μ mol) title complex 2 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 1.3ml triisobutyl aluminium modification again), make Al/Fe=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.63 * 10 4Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 7
1. the preparation of title complex 2 is with embodiment 5.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 2 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.91 * 10 5Gmol -1(Fe) h -1, oligomer content is respectively: C 498.7%, C 61.3%, be 99.8% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 8
1. the preparation of title complex 2 is with embodiment 5.
2. pressurization (1MPa) ethylene oligomerization: with the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 50ml toluene, the modification of 1.3ml triisobutyl aluminium), the toluene solution and the toluene of 20ml title complex 2 (5.0 μ mol) join in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.79 * 10 5Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 9
1.2-ethanoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) preparation of part [part 3]:: 2-ethanoyl-9-phenyl-1; 10-phenanthroline (0.295g; 1.0mol); 2; the 6-Diethyl Aniline (0.4482g, 2.5mmol) and the 96mg tosic acid in 20ml toluene, heating reflux reaction 21 hours; raw material reaction is complete; revolve to steam and remove toluene, residuum supports with methylene dichloride dissolving back neutral alumina, crosses the neutral alumina pillar; with petrol ether/ethyl acetate (10:1) drip washing; second flow point is a product, and with obtaining orange solids 0.24g after the ether washing drying, productive rate is 53.1% behind the evaporate to dryness.Fusing point is 256-258 ℃.
FT-IR(KBr?disc)：3061，2962，2924，2865，1635，1607，1589，1579，1546，1507，1486，1462，1436，1420，1381，1366，1294，1247，1189，1117，1097，860，780，761，741，685cm -1。
1H?NMR(400MHz，CDCl 3)：δ＝8.82(d，J＝8.4Hz，1H)；8.45(d，J＝7.6Hz，2H)；8.33(dd，J＝8.4Hz，2H)；8.17(d，J＝8.4Hz，1H)；7.88(d，J＝4.0Hz，2H)；7.56(t，J＝7.6Hz，2H)；7.47(t，J＝7.2Hz，1H)；7.21(d，J＝7.6Hz，2H)；7.13(t，J＝7.6Hz，1H)；2.86(sept，J＝6.8Hz，2H)；2.66(s，3H)；1.18(dd，J＝6.8Hz，12H)。
13C?NMR(75MHz，CDCl 3)：δ＝167.7，156.9，155.8，146.7，146.0，145.2，139.2，137.1，136.5，135.8，129.9，129.7，129.0，127.8，127.5，127.3，126.1，123.7，123.1，120.6，119.9，28.3，23.3，23.0，17.3。
Ultimate analysis (C 26H 27N 3) theoretical value (%): C83.99, H6.83, N9.18; Experimental value (%): C84.00, H6.84, N8.98.
2. the preparation that iron (II) [title complex 3] closed in chlorination [2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-diisopropyl aniline)]: with 2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-diisopropyl aniline) part (0.0918g, 0.2mmol) and FeCl 24H 2O (0.0401g 0.2mmol) places the Schlenk pipe, behind the vacuum nitrogen filling gas three times, adds the tetrahydrofuran (THF) of the 4ml degassing, and reaction solution is earlier by the very fast generation green precipitate of green solution, and stirring reaction is 9 hours under the room temperature, the gained sedimentation and filtration, and filtrate be green; Precipitation is with ether washing, dry shallow green powder 0.0776g, and productive rate is 66.2%.
FT-IR(KBr?disc)：3062，2969，2926，2865，1611，1590，1557，1501，1490，1463，1440，1374，1330，1286，1247，1185，1152，1138，870，786，748，701cm -1。
Ultimate analysis (C 32H 31Cl 2FeN 3) theoretical value (%): C65.77, H5.35, N7.19; Experimental value (%): C65.15, H5.32, N6.95.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.9mg (5 μ mol) title complex 3 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: do not obtain oligopolymer.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 10
1. the preparation of title complex 3 is with embodiment 9.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.9mg (5 μ mol) title complex 3 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 1.3ml triisobutyl aluminium modification again), make Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.99 * 10 3G.mol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 11
1. the preparation of title complex 3 is with embodiment 9.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 3 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 6.21 * 10 3Gmol (Fe) -1H -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 12
1. the preparation of title complex 3 is with embodiment 9.
2. pressurization (1MPa) ethylene oligomerization: with the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 50ml toluene, the modification of 1.3ml triisobutyl aluminium), the toluene solution and the toluene of 20ml title complex 3 (5.0 μ mol) join in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.90 * 10 4Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 13
1.2-benzoyl-9-phenyl-1; the preparation of 10-phenanthroline: bromobenzene (3.2mL; 30.5mmol) diethyl ether solution (20mL) be added drop-wise to 2 normal metallic lithiums (439mg 63.2mmol) make phenyl lithium solution in the ether suspension (30mL) under room temperature and nitrogen protection.Under-78 ℃ and nitrogen protection, the above-mentioned phenyl lithium drips of solution that makes is added to 2-cyano group-1, (2.053g in toluene suspension 10.0mmol) (50mL), slowly rises to room temperature and stirs and spend the night the 10-phenanthroline after dropwising.Reaction is ended by slowly adding water, and red organic layer separates, and water layer merges organic phase subsequently and uses anhydrous sodium sulfate drying with dichloromethane extraction several times.Concentrate organic layer, residuum is crossed silica gel pillar purifying and is obtained yellow solid product 2-benzoyl-9-phenyl-1, and 10-phenanthroline 1.245g, productive rate are 21.3%.Fusing point is 162-164 ℃.
FT-IR(KBr?disc)：3060，3034，1645，1616，1595，1575，1545，1505，1486，1446，1420，1364，1319，1288，1183，1152，1093，1023，944，878，865，768，716，692cm -1。
1H?NMR(300MHz，CDCl 3)：δ＝8.93(d，J＝7.2Hz，2H)，8.55-8.39(m，4H)，8.30(d，J＝8.4Hz，1H)，8.16(d，J＝8.4Hz，1H)，7.89(d，J＝8.7Hz，1H)，7.81(d，J＝8.7Hz，1H)，7.72-7.62(m，3H)，7.56-7.49(m，3H)。
13C?NMR(100MHz，CDCl 3)：δ＝191.4，156.5，153.4，145.9，144.6，138.8，136.7，136.6，132.7，132.5，129.8，129.6，128.6，128.3，127.8，127.5，127.3，125.4，122.6，119.6。
Ultimate analysis (C 25H 16N 2O) theoretical value (%): C83.31, H4.47, N7.77; Experimental value (%): C82.94, H4.45, N7.73.
2.2-benzoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-xylidine) preparation of part [part 4]: 2-benzoyl-9-phenyl-1; 10-phenanthroline (0.76g; 2.1mmol) and 2; (0.585g 4.8mmol) adds the 100mg tosic acid and makes catalyzer the 6-xylidine, reacts 36 hours in about 140 ℃ in the 5ml tetraethoxy; and tell the ethanol of generation with water-and-oil separator; tetraethoxy is removed in decompression, and residuum supports parlkaline aluminum oxide pillar with the methylene dichloride dissolving; with petrol ether/ethyl acetate (6:1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.376g, and productive rate is 38.4%.Fusing point is 142-144 ℃.
FT-IR(KBr?disc)：3055，2943，1616，1589，1577，1544，1505，1484，1441，1368，1319，1290，1207，1088，1024，969，858，773，765，740，716，694cm -1。
1H?NMR(400MHz，CDCl 3)：δ＝8.87(d，J＝8.4Hz，1H)；8.37(d，J＝8.4Hz，1H)；8.26-8.24(m，3H)；8.11(d，J＝8.4Hz，1H)；7.82(s，2H)；7.57(d，J＝8.0Hz，2H)；7.46(t，J＝7.2Hz，4H)；7.38(t，J＝7.2Hz，2H)；6.96(d，J＝7.2Hz，2H)；6.86(t，J＝7.2Hz，1H)；2.12(s，6H)。
13C?NMR(100MHz，CDCl 3)：δ＝166.1，155.9，155.7，148.2，145.7，144.7，138.5，136.3，136.0，135.4，129.6，129.2，129.1，128.9，128.3，127.9，127.3，127.0，126.8，126.7，125.5，125.2，122.7，121.7，118.9，18.2。
Ultimate analysis (C 33H 25N 3) theoretical value (%): C85.50, H5.44, N9.06; Experimental value (%): C85.14, H5.47, N8.94.
3. chlorination [2-benzoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-xylidine)] preparation of closing iron (II) [title complex 4]: 2-benzoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-xylidine) (0.0698g is 0.15mmol) with 1 normal FeCl for part 24H 2O (0.0312g, 0.15mmol) place the Schlenk pipe, behind the vacuum nitrogen filling gas three times, the dehydrated alcohol that adds the 6ml degassing, reaction solution become green by yellow-green colour earlier and have the greyish-green precipitation to generate stirring reaction 12hrs under the room temperature, filter, filtrate is green, precipitates with ether washing, the dry greyish-green powder 0.0772g of getting, and productive rate is 86.9%.
FT-IR(KBr?disc)：3056，2922，1620，1588，1549，1489，1445，1368，1300，1212，1155，1001，863，774，744，703cm -1。
Ultimate analysis (C 33H 25Cl 2FeN 3H 2O) theoretical value (%): C65.15, H4.47, N6.91; Experimental value (%): C65.12, H4.11, N6.85.
4. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 4 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.95 * 10 3Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 14
1. the preparation of title complex 4 is with embodiment 13.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 4 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 1.3ml triisobutyl aluminium modification again), make Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.64 * 10 5Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 15
1. the preparation of title complex 4 is with embodiment 13.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 4 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.94 * 10 6Gmol -1(Fe) h -1, oligomer content is respectively: C 499.2%, C 60.8%, be 99.9% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 16
1. the preparation of title complex 4 is with embodiment 13.
2. pressurization (1MPa) ethylene oligomerization: with the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 50ml toluene, the modification of 1.3ml triisobutyl aluminium), the toluene solution and the toluene of 20ml title complex 4 (5.0 μ mol) join in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.11 * 10 6Gmol -1(Fe) h -1, oligomer content is respectively: C 499.1%, C 60.9%, be 100% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 17
1.2-benzoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) preparation of part [part 5]:: 2-benzoyl-9-phenyl-1; 10-phenanthroline (0.57g; 1.58mmol) and 2; (0.4978g 3.27mmol) adds the 112mg tosic acid and makes catalyzer the 6-Diethyl Aniline, reacts 12 hours in about 140 ℃ in the 5ml tetraethoxy; and tell the ethanol of generation with water-and-oil separator; tetraethoxy is removed in decompression, and residuum supports parlkaline aluminum oxide pillar with the methylene dichloride dissolving; with petrol ether/ethyl acetate (4:1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.5664g, and productive rate is 72.8%.Fusing point is 187-189 ℃.
FT-IR(KBr?disc)：3060，3034，2962，2918，1618，1586，1542，1504，1485，1440，1363，1294，1200，1090，965，869，763，697cm -1。
1H?NMR(400MHz，CDCl 3)：δ＝8.85(d，J＝8.0Hz，1H)；8.37-8.22(m，4H)；8.09(d，J＝8.0Hz，1H)；7.80(s，2H)；7.58(s，2H)；7.45-7.36(m，6H)；7.01-6.97(m，3H)；2.61(q，J＝7.2Hz，2H)；2.34(q，J＝7.2Hz，2H)；1.16(t，J＝7.2Hz，6H)。
13C?NMR(100MHz，CDCl 3)：δ＝165.7，156.2，156.1，147.6，146.1，145.1，138.9，136.7，136.4，135.4，131.1，130.3，129.6，129.2，128.7，128.5，127.7，127.5，127.3，127.2，125.8，125.5，123.4，122.1，119.2，24.5，13.5。
Ultimate analysis (C 35H 29N 3) theoretical value (%): C85.51, H5.95, N8.55; Experimental value (%): C85.03, H5.94, N8.48.
2. the preparation that iron (II) [title complex 5] closed in chlorination [2-benzoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-Diethyl Aniline)]: 2-benzoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-Diethyl Aniline) part (0.0745g, 0.15mmol) and FeCl 24H 2O (0.0310g, 0.15mmol) place the Schlenk pipe, behind the vacuum nitrogen filling gas three times, the dehydrated alcohol that adds the 5ml degassing, reaction solution become green by yellow-green colour earlier and have the dark-brown precipitation to generate stirring reaction 9hrs under the room temperature, filter, filtrate is green, precipitates with ether washing, the dry dark-brown powder 0.0673g of getting, and productive rate is 71.8%.
FT-IR(KBr?disc)：3061，2966，2874，1594，1553，1490，1444，1368，1291，1261，1107，1059，1000，868，781，702cm -1。
Ultimate analysis (C 35H 29Cl 2FeN 3) theoretical value (%): C67.98, H4.73, N6.80; Experimental value (%): C67.94, H4.78, N6.57.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 5 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out GC and analyze: the active 520gmol of being of oligomerisation -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 18
1. the preparation of title complex 5 is with embodiment 17.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 5 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 1.3ml triisobutyl aluminium modification again), make Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.13 * 10 4Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 19
1. the preparation of title complex 5 is with embodiment 17.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 5 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 5.16 * 10 5Gmol -1(Fe) h -1, oligomer content is respectively: C 498.6%, C 61.4%, be 100% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 20
1. the preparation of title complex 5 is with embodiment 17.
2. pressurization (1MPa) ethylene oligomerization: with the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 50ml toluene, the modification of 1.3ml triisobutyl aluminium), the toluene solution and the toluene of 20ml title complex 5 (5.0 μ mol) join in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 5.43 * 10 5Gmol (Fe) -1H -1, oligomer content is respectively: C 498.7%, C 61.3%, be 100% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 21
1.2-benzoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) preparation of part [part 6]: 2-benzoyl-9-phenyl-1; 10-phenanthroline (0.3938g; 1.09mmol) and 2; (0..4328g 2.44mmol) adds the 112mg tosic acid and makes catalyzer the 6-diisopropyl aniline, reacts 12 hours in about 140 ℃ in the 5ml tetraethoxy; and tell the ethanol of generation with water-and-oil separator; tetraethoxy is removed in decompression, and residuum supports parlkaline aluminum oxide pillar with the methylene dichloride dissolving; with petrol ether/ethyl acetate (6:1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.42g, and productive rate is 74.0%.Fusing point is 170-171 ℃.
FT-IR(KBr?disc)：3063，2958，2860，1611，1588，1544，1506，1487，1463，1430，1358，1291，1194，1091，966，858，777，757，701cm -1。
1H?NMR(300MHz，CDCl 3)：δ＝8.84(d，J＝7.2Hz，1H)；8.38-8.24(m，4H)；8.11(d，J＝8.4Hz，1H)；7.82(s，2H)；7.62(s，2H)；7.49-7.39(m，6H)；7.04(s，3H)；3.00(m，2H)；1.19(s，6H)；0.97(s，6H)。
13C?NMR(100MHz，CDCl 3)：δ＝164.9，155.9，145.7，144.6，138.5，136.3，136.0，135.2，134.5，130.3，129.1，128.7，128.4，128.2，128.1，127.2，127.1，126.9，126.7，125.4，123.2，122.4，121.8，111.8，28.1，23.7，21.6。
Ultimate analysis (C 37H 33N 3) theoretical value (%): C85.51, H6.40, N8.09; Experimental value (%): C84.91, H6.36, N7.84.
2. chlorination [2-benzoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-diisopropyl aniline)] preparation of closing iron (II) [title complex 6]: 2-benzoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) part (0.0795g, 0.15mmol) and FeCl 24H 2O (0.0309g, 0.15mmol) place the Schlenk pipe, behind the vacuum nitrogen filling gas three times, the dehydrated alcohol that adds the 5ml degassing, reaction solution become green by yellow-green colour earlier and have the generation of brown-green precipitation to become taupe afterwards, stirring reaction 12hrs under the room temperature, filter, filtrate is green, precipitates with ether washing, the dry brown ceramic powder 0.0856g of getting, and productive rate is 86.6%.
FT-IR(KBr?disc，cm -1)：3031，2959，2866，1620，1587，1550，1488，1459，1436，1364，1319，1274，1206，995，872，850，704。
Ultimate analysis (C 37H 33Cl 2FeN 3) theoretical value (%): C68.75, H5.15, N6.50; Experimental value (%): C68.42, H5.23, N6.59.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.2mg (5 μ mol) title complex 6 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: do not have the oligomerisation activity.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 22
1. the preparation of title complex 6 is with embodiment 21.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.2mg (5 μ mol) title complex 6 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 1.7ml triisobutyl aluminium modification again), make Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.75 * 10 3Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 23
1. the preparation of title complex 6 is with embodiment 21.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 6 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.09 * 10 3Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 24
1. the preparation of title complex 6 is with embodiment 21.
2. pressurization (1MPa) ethylene oligomerization: with the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 50ml toluene, the modification of 1.3ml triisobutyl aluminium), the toluene solution and the toluene of 20ml title complex 6 (5.0 μ mol) join in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.65 * 10 3Gmol -1(Fe) h -1, oligomerization product has only 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 25
1. chlorination [2-ethanoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-xylidine)] preparation of closing cobalt (II) [title complex 7]: with 2-ethanoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-xylidine) (0.0806g is 0.2mmol) with anhydrous CoCl for part 2(0.0274g 0.2mmol) places the Schlenk pipe, adds the 4ml dehydrated alcohol, solution is green during beginning, and is just muddy gradually and generate green precipitate, at room temperature stirred 12 hours, filtration obtains green powder 0.07g after with ether washing, drying, and productive rate is 65.6%.
FT-IR(KBr?disc，cm -1)：3063，2945，2914，1619，1585，1557，1504，1490，1451，1437，1374，1290，1256，1206，1142，989，919，865，791，772，745，700，653，609。
Ultimate analysis (C 28H 23Cl 2CoN 3H 2O) theoretical value (%): C61.22, H4.59, N7.65; Experimental value (%): C61.46, H4.34, N7.24.
Its crystalline structure as shown in Figure 3.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) title complex 7 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 6.85 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 494.3%, C 65.7%, be 97.0% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 26
1. the preparation of title complex 7 is with embodiment 25.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 7 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Co=500.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.32 * 10 6Gmol (Co) -1H -1, oligomer content is respectively: C 492.1%, C 67.6%, be 99.8% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 27
1. chlorination [2-ethanoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-Diethyl Aniline)] preparation of closing cobalt (II) [title complex 8]: with 2-ethanoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) (0.065g is 0.15mmol) with anhydrous CoCl for part 2(0.0207g 0.16mmol) places the Schlenk pipe, adds the 4ml dehydrated alcohol, and solution is green during beginning, and very fast generation green precipitate at room temperature stirs 12h, filters with obtaining green powder 0.068g after ether washing, the drying, and productive rate is 80.3%.
FT-IR(KBr?disc)：3061，2969，2924，2865，1613，1582，1557，1501，1489，1463，1441，1375，1330，1288，1185，1153，869，786，749，700cm -1。
Ultimate analysis (C 30H 27Cl 2CoN 3) theoretical value (%): C64.41, H4.86, N7.51; Experimental value (%): C64.25, H4.92, N7.27
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.8mg (5 μ mol) title complex 8 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 6.71 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 491.9%, C 65.4%, C 〉=82.7%, be 97.9% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 28
1. the preparation of title complex 8 is with embodiment 27.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 8 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Co=500.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.06 * 10 6Gmol -1(Co) h -1, oligomer content is respectively: C 495.7%, C 64.0%, C 〉=80.3%, be 99.7% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 29
1. chlorination [2-ethanoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-diisopropyl aniline)] preparation of closing cobalt (II) [title complex 9]: with 2-ethanoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) (0.0937g is 0.2mmol) with anhydrous CoCl for part 2(0.0279g 0.21mmol) places the Schlenk pipe, adds the 6ml dehydrated alcohol, and solution is green during beginning, and very fast generation green precipitate at room temperature stirs 24h, filters with obtaining green powder 0.103g after ether washing, the drying, and productive rate is 85.6%.
FT-IR(KBr?disc)：3450，3062，2964，2932，2875，1618，1585，1558，1504，1490，1441，1375，1290，1193，859，787，760，745，701cm -1。
Ultimate analysis (C 32H 31Cl 2CoN 3) theoretical value (%): C65.43, H5.32, N7.15; Experimental value (%): C64.48, H5.55, N6.61.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.9mg (5 μ mol) title complex 9 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.23 * 10 5Gmol (Co) -1H -1, oligomer content is respectively: C 480.0%, C 616.5%, C 〉=83.5%, be 95.4% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 30
1. the preparation of title complex 9 is with embodiment 29.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 9 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Co=500.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 6.52 * 10 6Gmol -1(Co) h -1, oligomer content is respectively: C 475.7%, C 623.0%, C 〉=81.3%, be 99.7% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 31
1. chlorination [2-benzoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-xylidine)] preparation of closing cobalt (II) [title complex 10]: with 2-benzoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-xylidine) (0.0696g is 0.15mmol) with anhydrous CoCl for part 2(0.0212g 0.15mmol) places the Schlenk pipe, adds the 6ml dehydrated alcohol, solution is green during beginning, after generate the brown precipitation gradually, at room temperature stir 15h, filtration obtains sorrel powder 0.0714g after with ether washing, drying, and productive rate is 80.2%.
FT-IR(KBr?disc)：3057，2919，1612，1597，1555，1490，1445，1371，1317，1289，1213，999，863，774，748，721，703cm -1。
Ultimate analysis (C 33H 25Cl 2CoN 3CH 2Cl 2) theoretical value (%): C60.20, H4.01, N6.19; Experimental value (%): C60.25, H4.02, N6.28.
Its crystalline structure as shown in Figure 4.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.9mg (5 μ mol) title complex 10 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.58 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 484.4%, C 614.8%, C 〉=80.8%, be 96.4% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 32
1. the preparation of title complex 10 is with embodiment 31.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 10 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Co=500.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.90 * 10 6Gmol -1(Co) h -1, oligomer content is respectively: C 484.5%, C 613.4%, C 〉=82.1%, be 99.8% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 33
1. chlorination [2-benzoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-Diethyl Aniline)] preparation of closing cobalt (II) [title complex 11]: with 2-benzoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) (0.0856g is 0.174mmol) with anhydrous CoCl for part 2(0.0268g 0.2mmol) places the Schlenk pipe, adds the 8ml dehydrated alcohol, and solution be green during beginning, after generate the brown precipitation gradually, at room temperature stir 12h, filter with ether and wash, obtain Vandyke brown powder 0.084g after the drying, productive rate is 77.6%.
FT-IR(KBr?disc)：3063，2963，2934，2875，1613，1596，1552，1498，1490，1442，1371，1319，1288，1108，995，872，782，751，720，701cm -1。
Ultimate analysis (C 35H 29Cl 2CoN 3CH 2Cl 2) theoretical value (%): C61.21, H4.42, N5.95; Experimental value (%): C60.68, H4.28, N5.63.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 0.25ml diethylaluminum chloride solution (hexane solution of 2.0mol/l) again, makes Al/Co=100.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: do not have the oligomerisation activity.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 34
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 0.5ml diethyl aluminum chloride solution (hexane solution of 2.0mol/l) again, makes Al/Co=200.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: do not have the oligomerisation activity.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 35
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 1.3ml triisobutyl aluminium modification again), make Al/Co=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.93 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 477.1%, C 616.2%, C 〉=86.7%, be 96.1% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 36
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 0.35ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=100.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 0.76 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 490.7%, C 65.9%, C 〉=83.4%, be 98.0% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 37
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 0.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=200.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.33 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 486.3%, C 610.6%, C 〉=83.1%, be 97.0% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 38
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 6.42 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 478.5%, C 615.2%, C 〉=86.3%, be 96.7% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 39
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 3.4ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=1000.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.70 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 477.8%, C 615.1%, C 〉=87.1%, be 97.4% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 40
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 5.1ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=1500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.42 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 476.0%, C 616.7%, C 〉=87.3%, be 96.1% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 41
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 6.8ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=2000.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.31 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 482.2%, C 614.8%, C 〉=83.0%, be 98.2% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 42
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 0 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.64 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 491.0%, C 67.6%, C 〉=81.4%, be 98.4% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 43
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.05 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 481.1%, C 616.0%, C 〉=82.9%, be 95.9% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 44
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 60 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.41 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 472.4%, C 619.2%, C 〉=88.4%, be 97.2% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 45
1. the preparation of title complex 11 is with embodiment 33.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 80 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 0.874 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 472.5%, C 616.6%, C 〉=810.9%, be 96.3% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 46
1. the preparation of title complex 11 is with embodiment 33.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 11 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Co=500.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 7.33 * 10 6Gmol -1(Co) h -1, oligomer content is respectively: C 480.5%, C 616.8%, C 〉=82.7%, be 99.7% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 47
1. chlorination [2-benzoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-diisopropyl aniline)] preparation of closing cobalt (II) [title complex 12]: with 2-benzoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) (0.0785g is 0.15mmol) with anhydrous CoCl for part 2(0.021g 0.15mmol) places the Schlenk pipe, adds the 6ml dehydrated alcohol, and solution be green during beginning, after generate the brown precipitation gradually, at room temperature stir 12h, filter with ether and wash, obtain sorrel powder 0.0769g after the drying, productive rate is 78.4%.
FT-IR(KBr?disc)：3058，3032，2959，2924，2865，1619，1599，1552，1489，1437，1370，1319，1274，1207，1100，995，873，850，759，718，652cm -1。
Ultimate analysis (C 37H 33Cl 2CoN 3CH 2Cl 2) theoretical value (%): C62.14, H4.80, N5.72; Experimental value (%): C62.17, H4.82, N5.54.
Its crystalline structure as shown in Figure 5.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.2mg (5 μ mol) title complex 12 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.85 * 10 5Gmol -1(Co) h -1, oligomer content is respectively: C 455.2%, C 628.1%, C 〉=816.7%, be 94.3% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 48
1. the preparation of title complex 12 is with embodiment 47.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l), 20ml title complex 12 (5.0 μ mol) are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Co=500.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.80 * 10 6Gmol -1(Co) h -1, oligomer content is respectively: C 446.7%, C 634.0%, C 〉=819.3%, be 100% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 49
1. the preparation that nickel (II) [title complex 13] closed in chlorination [2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-xylidine)]: with 2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-xylidine) part (0.0957g, 0.238mmol) and NiCl 26H 2(0.0602g 0.251mmol) places the Schlenk pipe to O, adds the 10ml dehydrated alcohol, and very fast generation precipitation at room temperature stirred 15 hours, and the gained sedimentation and filtration is obtained orange powder 0.1131g after with ether washing, drying, and productive rate is 89.3%.
FT-IR(KBr?disc)：3445，3056，1611，1587，1556，1503，1489，1453，1376，1294，1204，1148，862，793，773，745，702cm -1。
Ultimate analysis (C 28H 23Cl 2N 3Ni1/2CH 2Cl 2) theoretical value (%): C59.68, H4.22, N7.33; Experimental value (%): C59.89, H4.44, N7.20.
Its crystalline structure as shown in Figure 6.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) title complex 13 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.74 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 498.0%, C 62.0%, be 17.5% to the selectivity of 1-butylene.Prolong and react to 60min: the oligomerisation activity is 3.49 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 496.7%, C 63.3%, be 4.3% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 50
1. the preparation of title complex 13 is with embodiment 49.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 13 (5.0 μ mol) and 100 μ mol triphenylphosphines is joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.68 * 10 6Gmol -1(Ni) h -1, oligomer content is respectively: C 498.1%, C 61.9%, be 36.2% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 51
1. the preparation that nickel (II) [title complex 14] closed in chlorination [2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-Diethyl Aniline)]: with 2-ethanoyl-9-phenyl-1,10-phenanthroline (contracting 2, the 6-Diethyl Aniline) part (0.0779g, 0.18mmol) and NiCl 26H 2(0.0458g 0.19mmol) places the Schlenk pipe to O, adds the 10ml dehydrated alcohol, the orange precipitation of very fast generation at room temperature stirs 15hrs, with the gained sedimentation and filtration, filtrate is yellow, precipitates with ether washing, the dry orange powder 0.091g of getting, and productive rate is 89.7%.
FT-IR(KBr?disc)：3442，3062，2958，2871，1616，1584，1559，1502，1489，1442，1377，1302，1292，1192，1060，859，787，762，744，701cm -1。
Ultimate analysis (C 30H 27Cl 2N 3Ni1/2CH 2Cl 2) theoretical value (%): C60.89, H4.69, N6.98; Experimental value (%): C60.46, H4.96, N6.67.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.8mg (5 μ mol) title complex 13 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.29 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 497.3%, C 62.7%, be 15.9% to the selectivity of 1-butylene.Prolong and react to 60min: the oligomerisation activity is 4.67 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 497.0%, C 63.0%, be 5.8% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 52
1. the preparation of title complex 14 is with embodiment 51.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 14 (5.0 μ mol) and 100 μ mol triphenylphosphines is joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 6.15 * 10 6Gmol -1(Ni) h -1, oligomer content is respectively: C 498.7%, C 61.3%, be 50.2% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 53
1. chlorination [2-ethanoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-diisopropyl aniline)] preparation of closing nickel (II) [title complex 15]: with 2-ethanoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) part (0.0933g, 0.204mmol) and NiCl 26H 2O (0.0494g 0.206mmol) places the Schlenk pipe, adds the 5ml dehydrated alcohol, at room temperature stirs 15hrs, the orange sedimentation and filtration of generation after with ether washing, drying orange powder 0.0916g, productive rate is 76.5%.
FT-IR(KBr?disc)：3426，3060，2967，2865，1609，1586，1558，1489，1443，1378，1330，1293，1185，1151，869，787，761，749，702cm -1。
Ultimate analysis (C 32H 31Cl 2N 3NiCH 2Cl 2) theoretical value (%): C58.97, H4.95, N6.25; Experimental value (%): C58.44, H5.02, N6.20.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 2.9mg (5 μ mol) title complex 15 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.33 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 497.5%, C 62.5%, be 14.0% to the selectivity of 1-butylene.Prolong and react to 60min: the oligomerisation activity is 3.68 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 496.1%, C 63.9%, be 3.2% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 54
1. the preparation of title complex 15 is with embodiment 53.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 15 (5.0 μ mol) and 100 μ mol triphenylphosphines is joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.96 * 10 6Gmol -1(Ni) h -1, oligomer content is respectively: C 498.9%, C 61.1%, be 63.4% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 55
1. chlorination [2-benzoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-xylidine)] preparation of closing nickel (II) [title complex 16]: with 2-benzoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-xylidine) part (0.0936g, 0.202mmol) and NiCl 26H 2O (0.0491g 0.205mmol) places the Schlenk pipe, adds the 5ml dehydrated alcohol, stirring reaction 15hrs at room temperature, and with the gained sedimentation and filtration, filtrate be yellow, and precipitation is with ether washing, the dry yellow powder 0.115g that gets, and productive rate is 96.0%.
FT-IR(KBr?disc)：3388，1618，1592，1554，1486，1445，1378，1290，1212，1057，1038，1004，868，778，754，723，703cm -1。
Ultimate analysis (C 33H 25Cl 2N 3NiH 2O) theoretical value (%): C64.85, H4.45, N6.88; Experimental value (%): C65.09, H4.16, N6.82.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 16 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.47 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 497.8%, C 62.2%, be 15.2% to the selectivity of 1-butylene.Prolong and react to 60min: the oligomerisation activity is 4.71 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 495.7%, C 64.3%, be 2.8% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 56
1. the preparation of title complex 16 is with embodiment 55.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 16 (5.0 μ mol) and 100 μ mol triphenylphosphines are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.91 * 10 6Gmol -1(Ni) h -1, oligomer content is respectively: C 498.1%, C 61.9%, be 38.9% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 57
1. chlorination [2-benzoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline)] close the preparation of nickel (II) [title complex 17]: with 2-benzoyl-9-phenyl-1; the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) part (0.0987g; 0.201mmol) be suspended in the 4ml dehydrated alcohol, to wherein dripping 4ml NiCl 26H 2O (0.0496g, ethanolic soln 0.209mmol) have just begun not have considerable change, after become orangely gradually by yellow, stirring at room reaction 9hrs filters, filtrate be yellow, precipitation is with ether washing, the dry orange powder 0.113g that gets, productive rate is 90.6%.
FT-IR(KBr?disc)：3061，2963，1597，1558，1489，1443，1377，1291，1209，1148，1108，1065，1040，1004，867，784，706cm -1。
Ultimate analysis (C 35H 29Cl 2N 3Ni1/2CH 2Cl 2) theoretical value (%): C64.24, H4.56, N6.33; Experimental value (%): C64.50, H4.75, N6.60.
Its crystalline structure as shown in Figure 7.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 17 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Ni=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: do not have the oligomerisation activity.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 58
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 17 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 1.7ml methylaluminoxane (MAO) (toluene solution of 1.46mol/l) again, makes Al/Ni=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: do not have the oligomerisation activity.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 59
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 17 and then vacuumize and with ethene displacement 3 times.With the toluene of syringe injection 30ml, add the n-heptane solution of methylaluminoxane (MMAO) 1.93mol/l of 1.7ml triisobutyl aluminium modification again), make Al/Ni=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.8 * 10 3Gmol -1(Ni) h -1, oligomerization product has only butylene, is 92.8% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 60
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 17 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.With the toluene of syringe injection 30ml, add the methylaluminoxane (MMAO) (n-heptane solution of 1.93mol/l) of 1.7ml modification again, make Al/Ni=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.28 * 10 4Gmol -1(Ni) h -1, oligomerization product has only butylene, is 41.6% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 61
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 17, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.43 * 10 4Gmol -1(Ni) h -1, oligomerization product has only butylene, is 78.5% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 62
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 17 and 10 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 9.63 * 10 4Gmol -1(Ni) h -1, oligomer content is respectively: C 497.8%, C 62.2%, be 27.1% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 63
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 17 and 25 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.29 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 498.1%, C 61.9%, be 24.0% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 64
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 17 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.31 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 498.1%, C 61.9%, be 15.9% to the selectivity of 1-butylene.Prolong and react to 60min: the oligomerisation activity is 3.71 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 496.5%, C 63.5%, be 3.5% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 65
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 17 and 100 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 6.82 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 497.7%, C 62.3%, be 8.5% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 66
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 17 and 100 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.75 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 498.8%, C 61.2%, be 27.2% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 67
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) title complex 17 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 0 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.14 * 10 5Gmol (Ni) -1H -1, oligomer content is respectively: C 499.2%, C 60.8%, be 34.6% to the selectivity of 1-butylene.Prolong and react to 60min: the oligomerisation activity is 1.91 * 10 5Gmol (Co) -1H -1, oligomer content is respectively: C 498.4%, C 61.6%, be 16.3% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 68
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 17 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.36 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 497.2%, C 62.8%, be 22.7% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 69
1. the preparation of title complex 17 is with embodiment 57.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 17 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 60 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.58 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 495.4%, C 64.6%, be 20.2% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 70
1. the preparation of title complex 17 is with embodiment 57.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 17 (5.0 μ mol) is joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.26 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 498.9%, C 61.1%, be 97.1% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 71
1. the preparation of title complex 17 is with embodiment 57.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 17 (5.0 μ mol) and 50 μ mol triphenylphosphines are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 5.87 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 4100%, be 93.0% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 72
1. the preparation of title complex 17 is with embodiment 57.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 17 (5.0 μ mol) and 50 μ mol triphenylphosphines are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 5.17 * 10 6Gmol -1(Ni) h -1, oligomer content is respectively: C 497.5%, C 62.5%, be 36.5% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 73
1. chlorination [2-benzoyl-9-phenyl-1; 10-phenanthroline (contracting 2, the 6-diisopropyl aniline)] preparation of closing nickel (II) [title complex 18]: with 2-benzoyl-9-phenyl-1, the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) part (0.0827g, 0.159mmol) and NiCl 26H 2O (0.0401g 0.168mmol) places the Schlenk pipe, adds the 10ml dehydrated alcohol, stirring reaction 15hrs at room temperature, and with the gained sedimentation and filtration, filtrate be yellow, and precipitation is with ether washing, the dry orange powder 0.0776g that gets, and productive rate is 75.1%.
FT-IR(KBr?disc)：3440，3057，2962，2866，1621，1595，1554，1490，1439，1377，1322，1293，1207，1151，1101，1024，872，784，763，707cm -1。
Ultimate analysis (C 37H 33Cl 2N 3Ni0.5CH 2Cl 2) theoretical value (%): C65.11, H4.95, N6.07; Experimental value (%): C65.01, H5.04, N5.85.
2. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of successive drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) title complex 16 and 50 μ mol triphenylphosphines, and then vacuumize and replace 3 times with ethene.Toluene with syringe injection 30ml adds 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l) again, makes Al/Ni=300.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.88 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 497.5%, C 62.5%, be 10.6% to the selectivity of 1-butylene.Prolong and react to 60min: the oligomerisation activity is 3.89 * 10 5Gmol -1(Ni) h -1, oligomer content is respectively: C 496.4%, C 63.6%, be 6.6% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 74
1. the preparation of title complex 18 is with embodiment 73.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution and the toluene of 50ml toluene, 0.75ml diethylaluminum chloride (hexane solution of 2.0mol/l), 20ml title complex 18 (5.0 μ mol) and 0.1mmol triphenylphosphine are joined in the stainless steel autoclave of 250-ml successively, making cumulative volume is 100ml, Al/Ni=300.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction finishes the back relief pressure, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 5.77 * 10 6Gmol -1(Ni) h -1, oligomer content is respectively: C 498.4%, C 61.6%, be 34.9% to the selectivity of 1-butylene.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.

Claims (7)

1. the 2-of formula I structure imido grpup-9-phenyl-1, the 10-phenanthroline transient metal complex is characterized in that: described title complex is M, R and R 1Be selected from the title complex of following any one combination:
Figure FSB00000541623800011
(formula I);
M＝Fe，R＝Me，R 1＝Me； M＝Fe，R＝Me，R 1＝Et；
M＝Fe，R＝Me，R 1＝iPr；?M＝Fe，R＝Ph，R 1＝Me；
M＝Fe，R＝Ph，R 1＝Et； M＝Fe，R＝Ph，R 1＝iPr；
M＝Co，R＝Me，R 1＝Me； M＝Co，R＝Me，R 1＝Et；
M＝Co，R＝Me，R 1＝iPr；?M＝Co，R＝Ph，R 1＝Me；
M＝Co，R＝Ph，R 1＝Et； M＝Co，R＝Ph，R 1＝iPr；
M＝Ni，R＝Me，R 1＝Me； M＝Ni，R＝Me，R 1＝Et；
M＝Ni，R＝Me，R 1＝iPr；?M＝Ni，R＝Ph，R 1＝Me；
M＝Ni，R＝Ph，R 1＝Et； M＝Ni，R＝Ph，R 1＝iPr；
Here, the Me represent methylidene, Et represents ethyl, and iPr represents sec.-propyl, and Ph represents phenyl.
2. the described 2-imido grpup of claim 1-9-phenyl-1, the preparation method of 10-phenanthroline transient metal complex comprises the steps:
1) with the tosic acid is catalyzer, with 2-ethanoyl-9-phenyl-1,10-phenanthroline or 2-benzoyl-9-phenyl-1, aniline reaction Synthetic 2-imido grpup-9-phenyl-1 that 10-phenanthroline and alkyl replace, 10-phenanthroline part;
2) with the 2-imido grpup-9-phenyl-1 that obtains in the step 1), 10-phenanthroline part and transition metal reactant salt can obtain described title complex.
3. catalyst composition, comprise Primary Catalysts and promotor, described Primary Catalysts is the described 2-imido grpup of claim 1-9-phenyl-1, and 10-phenanthroline transient metal complex, described promotor are selected from aikyiaiurnirsoxan beta, alkylaluminium cpd and chlorination aluminum alkyls;
Described aikyiaiurnirsoxan beta is the methylaluminoxane of methylaluminoxane, modification; Aluminum alkyls is trimethyl aluminium, triethyl aluminum; The chlorination aluminum alkyls is diethylaluminum chloride, ethylaluminium dichloride.
4. catalyst composition according to claim 3 is characterized in that: the mol ratio of metallic aluminium and Primary Catalysts central metal M is 100 to 2000 in the described promotor.
5. catalyst composition according to claim 3 is characterized in that: described catalyst composition also contains triphenylphosphine; The mol ratio of described triphenylphosphine and Primary Catalysts is 50-1: 1.
6. the application of the described catalyst composition of claim 3 in the catalyzed ethylene oligomerisation reaction.
7. application according to claim 6 is characterized in that: the temperature of described oligomerisation reaction is 20 to 80 ℃, and ethylene pressure is 10-0.1MPa.
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