CN1218785A - Olefine polymerization or tripolymerization method - Google Patents

Abstract

Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support to trimerize and/or polymerize olefins.

Description

Olefinic polymerization or trimeric method

The present invention relates to be used for alkene carry out trimerization and (or) chrome catalysts of polymerization.The present invention also relates to a kind of make alkene carry out trimerization and (or) method of polymerization.

The chromium oxide catalyst of band carrier is a principal element during olefin polymer (as the multipolymer of polyethylene or ethene and hexene) is made.These catalyzer can be used for various polymerization processs.But most of known chromium cpds must be with carrier just to have catalytic activity.And the chromium cpd of great majority band carrier only can be used for the polymerization of alkene.If the acquisition olefin copolymer just must add two kinds of different monomers in the polymerization reactor, so just make polymerization process become more complicated.

The catalyzer that is used for the alkene terpolymerization also is known technically, but these catalyzer lack the desired product selectivity that obtains, thereby the productive rate of product is also low.Yet the terpolymerization of alkene if can be carried out effectively, is still a kind of method that provides the alkene of usefulness, and the alkene of gained can further carry out terpolymerization, maybe can use it for polyreaction.

An object of the present invention is to provide and a kind ofly make alkene carry out trimeric to improve one's methods.

A further object of the present invention provides a kind of alkene that makes and carries out the polymeric method.

A further object of the invention provides a kind of catalyzer that is used for the improvement of alkene terpolymerization.

Another object of the present invention provides a kind of catalyzer that is used for olefinic polymerization.

Therefore, according to the present invention, the novel chromium cpd that contains is to prepare with the reaction mixture that comprises chromic salts, metal amide and any electron pair donor(EPD) solvent (for example ether).

According to another embodiment of the present invention, this contains chromium cpd, or the band carrier or not with carrier all can be used for make alkene carry out trimerization or polymerization.

Fig. 1 is product I-Cr that computer produces, records with monocrystalline X-ray crystallography method ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄The structural representation or the structural formula of the ball of-molecule-bar type projection or simplification, wherein chromium atom is an exception, it is represented with thermal ellipsoid.

Fig. 2 is the ball-bar type projection or the structural representation of the further simplification of same molecule shown in Figure 1, and wherein chromium atom is an exception, and it is represented with thermal ellipsoid.

Fig. 3 is product III-Cr (NC that computer produces, records with monocrystalline X-ray crystallography method ₄H ₄The Ortep figure of)-molecular structure, or structural representation or the structural formula simplified.

Fig. 4 is the ball-bar type projection or the structural representation of the further simplification of same molecule shown in Figure 3, and wherein chromium atom is an exception, and it is represented with thermal ellipsoid, but has shown among the figure that chemical formula is Cr (NC ₄H ₄) ₄Na ₂2OC ₄H ₈The wholly crystalline texture formula lattice of compound.

Fig. 5 is product IV-Cr (NC that computer produces, records with monocrystalline X-ray crystallography method ₄H ₄) ₅(OC ₄H ₈The Ortep figure of)-molecular structure, or structural representation or the structural formula simplified.

Fig. 6 is the ball-bar type projection or the structural representation of the further simplification of same molecule shown in Figure 5, and wherein chromium atom is an exception, and it is represented with thermal ellipsoid, but has shown among the figure that chemical formula is (Cr (NC ₄H ₄) ₅(OC ₄H ₈)) (Na) ₂4 (OC ₄H ₈) the wholly crystalline texture or the lattice of compound.

Fig. 7 is product V-Cr (NC that computer produces, records with monocrystalline X-ray crystallography method ₄H ₄) ₃Cl (O ₂C ₂H ₄(CH ₃) ₂) ₃The Ortep figure of Na-molecule comprises wholly crystalline texture or lattice.

Fig. 8 is the ball-bar type projection of the further simplification of same molecule shown in Figure 7.

Fig. 9 is Cr (NC ₄H ₄) ₃Cl (O ₂C ₂H ₄(CH ₃) ₂) ball-excellent projection of further simplification of compound, wherein chromium atom is an exception, it is represented with thermal ellipsoid.Molecule shown in the figure and Fig. 7 and shown in Figure 8 identical, but do not show wholly crystalline texture or lattice.

Chromium compound

Chromium compound of the present invention is best suited for the trimerization of alkene, also can be used for the polymerization of alkene, can be made by the reactant mixture that comprises chromic salts, metal chloride and any electron pair donor solvent (for example ether). In the present invention, the chromium compound of invention has the multiple title that can exchange, for example: invention or novel chromium compound, chromium complex, chromium pyrroles complex compound and (or) Chromium pyrrolate.

Chromic salts can be one or more organic chromic salts or inorganic chromate salts, and wherein the oxidation state of chromium is 0-6. The in the present invention definition of chromic salts also comprises crome metal. Generally, the chemical formula of chromic salts is CrXn, and X can be any organic group or inorganic based with can be different in the formula, and n is integer, and its value is 1-6. Typical organic group can contain about 1-20 carbon atom, and be selected from alkoxyl, ester group, ketone group and (or) acylamino-. Organic group can be: straight chain base or contain the base of side chain, cyclic group or acyclic radical, aryl or aliphatic group, and can by the aliphatic group that mixes, aryl and (or) the cyclic aliphatic base consists of. Typical inorganic based comprise halide, sulfate and (or) oxide, but be not limited to these.

Chromic salts is preferably halide, for example chromous bromide, chromic bromide, chromous iodide, iodate chromium, Chromous Fluoride, charomic fluoride, chromous chloride, chromium chloride and composition thereof. Chloride preferably, for example chromous chloride and (or) chromium chloride, this is because its cost is lower and the accessory substance (such as sodium chloride) of reaction is easy to separate.

The metal amide can be any can reaction with chromic salts and generate the metal amide of chromium-amide complex. General this metal amide can be any heterolytic fission or homolysis

Metal complex or salt, wherein acylamino-can be any nitrogenous organic group. The metal amide can or add it when reaction, or it is produced in the original place. General this metal amide contains 1-20 carbon atom approximately. Typical metal amide comprise primary amine and (or) amide of secondary amine, any alkali metal (the I A family in the periodic table comprises hydrogen) and (or) amide of any alkaline-earth metal (the XII A family in the periodic table), but be not limited to these. The hydrocarbyl portion system of the amic salt of metal is selected from the straight chain base or contains base, cyclic group or acyclic radical, aryl or the aliphatic group of side chain or the mixture of two or more above-mentioned base. The metal amide preferably is selected from the amide of the II A family metal of I A family (comprising hydrogen), because their halide easy and chromium reacts.

Typical preferred metal amide comprises: dimethylamino lithium, diethylamino lithium, lithium diisopropylamine, the dicyclohexyl Lithamide, two (trimethyl silyl) sodium amide, indoles sodium, the mixture of pyrrolesization sodium and two or more above-claimed cpd, but be not limited to these.Optimal in the metal amide is the pyrrolesization thing.In this manual, the pyrrolesization thing is meant and contains the nitrogenous heterocyclic compound of 5-atom, for example pyrroles, pyrrole derivative and composition thereof.Typical pyrrolesization system be selected from pyrroles, pyrrolesization lithium, pyrrolesization sodium, pyrrolesization potassium, pyrrolesization caesium and (or) the pyrrolesization thing salt that replaces, this is because they have good reactivity and activity to other reactants.The example of the pyrrolesization thing salt that replaces has 2,5-dimethyl pyrrole sodium and (or) 3,4-dimethyl pyrrole sodium, but be not limited to these.When used metal amide during for pyrrolesization thing ligand, the chromium cpd of generation is a Chromium pyrrolate.

The electron pair donor(EPD) solvent can be any electron pair donor(EPD) solvent that chromic salts and metal amide are reacted.Though we do not think bound by theory, but we think that still this electron pair donor(EPD) solvent can be a kind of reaction solvent, also may be a kind of reactant, typical electronic to give the body solvent have nitrogenous, contain oxygen, phosphorous and (or) compound of sulfur-bearing and (or) ether, but be not limited to these.

The example of typical nitrogenous compound has nitrile, as acetonitrile; Amine, as pyridine and (or) pyridine derivate; (or) amide, but be not limited to these.The typical nitrogenous compound of other comprise Nitromethane 99Min., lutidine, dimethyl formamide, N-methylformamide, aniline, oil of mirbane, tetramethyl-diamino methane, hexamethyldisilazane and (or) pyrrolidone, but be not limited to these.

Typical oxygenatedchemicals have acetone, ethyl acetate, methyl acetate, methyl alcohol, ethanol, methyl ethyl ketone, acetaldehyde, furans and (or) hexamethyldisiloxane, but be not limited to these.

Typical P contained compound have hexamethylphosphoramide, hexamethylphosphorictriamide, triethyl-phosphite, tributylphosphine oxide (TBPO) and (or) triethyl phosphine, but be not limited to these.

Typical sulfocompound have dithiocarbonic anhydride, methyl-sulphoxide, tetramethylene sulfone, thiophene and (or) methyl-sulfide or its mixture, but be not limited to these.

Ether in the reaction mixture can be one or more ether compounds that can impel chromic salts and metal amide to react.Though we do not think bound by theory, we think that still ether can be a kind of reaction solvent, also may be a kind of reactants.This ether can be any R-O-R of containing functional group aliphatic cpd and (or) aromatic substance, wherein the R base can be with can be different, but preferably are not that hydrogen, preferred ether are aliphatic ethers, this is for the purpose of safety, because aromatic oxide is deleterious to the people.In addition, preferred ether should be able to impel the halogenide of chromium and the pyrrolesization thing of I A family or II A family metal to react, and is easy to remove from reaction mixture.Typical ether compound has the mixture of tetrahydrofuran (THF), diox, diethyl ether, glycol dimethyl ether (glyme), diglyme, triglyme and two or more above-claimed cpd.Preferably ether is selected from tetrahydrofuran (THF), tetrahydrofuran derivatives, glycol dimethyl ether, glycol dimethyl ether derivative and composition thereof, and this is not only in for above-mentioned security consideration, but also since the amine salt that is suitable for can be dissolved in these ethers.

When preparing a kind of or a kind of novel chromium cpd, the consumption of each reactant can be with the kind of the chromium cpd product of desired acquisition and is different.The consumption that can be used to prepare every kind of reactant of novel chromium cpd all depends on the product of desired acquisition.Different reactive chemistry measurement Laws can produce different chromium cpds.For example, the reaction product of about 1 mole of chromium (II) and about 2 moles of pyrrolesization sodium is different from the reaction product of about 1 mole of chromium (II) and excessive pyrrolesization sodium.In addition, as previously mentioned,, can obtain different products even select different similar reactants for use.For example, select tetrahydrofuran (THF) or select for use glycol dimethyl ether can produce different reaction product for use.

Three kinds of reactants can be under the condition that is suitable for forming the solution that contains one or more chromium cpds of the present invention chemical combination by any way.Reaction should be carried out under the situation of anaerobic, therefore should for example nitrogen and (or) carry out under the such inert gas atmosphere of argon.Reaction pressure can adopt any liquid pressure of reactant maintenance that is enough to make.Generally, this pressure should be in the scope of about 1 normal atmosphere-3 normal atmosphere (101-303kPa). for ease of operation, generally adopt 1 normal atmosphere (101kPa).

Temperature of reaction can be that any ether that can make keeps liquid temperature.In order to make more effective the carrying out of reaction energy, temperature of reaction should preferably adopt the boiling point of ether near the boiling point of ether, makes reaction mixture refluxed for some time.

Reaction times can be the necessary any time that reacts.The reaction times newspaper is determined in kind, temperature of reaction and the reaction pressure of reactant.Can in the scope in 1 minute-2 week, change.The general reaction times was about 3 hours-5 days.Under top condition, the reaction times is about 3-48 hour.

After reaction was finished, known any method reclaimed solid reaction product on the available techniques.After reaction is finished, be preferably in and carry out any other and earlier reaction mixture is filtered before handling removing any byproduct of reaction such as salt (for example sodium-chlor), though not right and wrong do like this can not.Do like this is in order to quicken next step purification of chromium product.After the filtration, a kind of typical method that reclaims solid reaction product is to remove superfluous ether from reaction mixture.Known any method is removed on superfluous electron pair donor(EPD) solvent (as the ether) available techniques.The typical method of removing electron pair donor(EPD) solvent (as ether) have vacuum and (or) slowly evaporate under the condition of cleaning with nitrogen, but be not limited thereto.

Remove the additive method of electron pair donor(EPD) solvent (as ether) or can use separately, maybe can be used in combination.For example, reaction mixture can be filtered, carry out vacuum-drying then.Preferably reaction mixture is heated this temperature of maintenance slowly under the temperature of about 10 °-300 ℃ (preferably about 25 °-200 ℃), and under vacuum, remove superfluous electron pair donor(EPD) solvent (as ether) for the sake of security.The solid reaction product of gained is one or more chromium cpds of the present invention.

Another kind of way is that reaction mixture is filtered to remove any solid reaction by product, the reaction mixture after filtering with a kind of non-polar organic solvent processing then.Adding a kind of non-polar organic solvent can make one or more chromium cpds of the present invention form solid precipitation.Typical non-polar organic solvent has pentane, hexane, hexanaphthene, heptane and composition thereof, but is not limited to these.Preferably pentane is added in the reaction mixture after filtering, because pentane obtains easily and be easy to use.

Known any method reclaims on the chromium cpd precipitation available techniques of the present invention, and the simplest method is to filter.

As previously mentioned, the solid product of reaction mixture and generation will be in the atmosphere of anaerobic at any time, preferably is in the such inert atmosphere of nitrogen for example, because it is easy to obtain and is easy to use.

According to the present invention, the kind by changing used reactant and (or) consumption of every kind of reactant can make many chromium cpds.One or more novel chromium cpds that reclaim needn't through further purification just can be used for alkene trimerization and (or) polymerization.

Also known any method is purified chromium cpd on the available techniques.For example, one of the simplest method of purification is a solid with a kind of non-polar organic solvent (for example toluene) washing and recycling.The most handy a kind of nonpolar aliphatic organic solid can obtain best result like this.Typical cleaning solvent has pentane, hexane, hexanaphthene, heptane and composition thereof, but is not limited to these.Be good with pentane especially wherein.

Chromium cpd of the present invention as the trimerization of alkene and (or) can be with during the catalyzer of polymerization carrier and (or) be not with carrier.Known any method preparation on the chrome catalysts available techniques of band carrier.Any carrier of chrome catalysts that is applicable to all can use.Typically urge agent carrier to comprise inorganic oxide (or one or more combination), phosphatization inorganic oxide and composition thereof, but be not limited to this this.Particularly the carrier system that is suitable for is selected from silicon-dioxide, sial, aluminum oxide, fluorided alumina, aluminium oxide silicide, Thorotrast, aluminate or phosphate, aluminum phosphate, phosphatization silicon-dioxide, phosphatization aluminum oxide, silica-titania, co-precipitation earth silicon/titanic oxide and composition thereof, any or more than one above-mentioned carriers that can hold chromium all are suitable for, but according to present circumstances, with use fluoridize/aluminium oxide silicide is advisable.According to United States Patent (USP) the 4th, 364, No. 855 (1982) disclosed contents, present optimum support of the catalyst is an aluminate or phosphate, this is that the spy is quoted here because it has maximum terpolymerization activity.

Known any method preparation on the chrome catalysts system available techniques of band carrier.For example, the reaction mixture through filtering to remove any particulate state byproduct of reaction and to contain one or more new pyrrole chromium cpds is mixed with support of the catalyst, make it abundant contact.With needn't remove superfluous electron pair donor(EPD) solvent (as ether) before catalyzer contacts.But the words that need also can be dissolved in solid Chromium pyrrolate compound electron pair donor(EPD) solvent (as ether) again.This Chromium pyrrolate/ethereal solution generally is blueness or indigo plant/green, but also can be observed other colors.

Support of the catalyst is insoluble to ether/Chromium pyrrolate complex solution usually.The consumption of Chromium pyrrolate is just enough as long as surpass catalyst consumption.But general per 1 gram support of the catalyst is just enough with the Chromium pyrrolate compound about 5 grams at least.Every gram carrier should be used about 0.001-1 gram Chromium pyrrolate compound, the most handy about 0.01-0.5 gram Chromium pyrrolate compound, and the absorption of carrier is best like this, and the use of carrier and Chromium pyrrolate compound is the most effective.This mixture can be at any time, contact under the temperature and pressure and mix, so that the Chromium pyrrolate compound fully contacts with carrier.For ease of using, should adopt envrionment temperature and pressure.Mixing time was about 24 hours, was preferably 5 seconds about-10 hours, preferably was about 5 seconds-8 hours.Mixing time is longer generally can't bring more benefit, but the shorter then deficiency of mixing time so that the Chromium pyrrolate compound fully contact with carrier.

Add carrier and make it and the Chromium pyrrolate thorough mixing after filter, vacuum-drying, then activating compounds is added in the mixture of carrier and Chromium pyrrolate, this activating compounds be generally one or more Lewis acids and (or) solution of metal alkylide, the preferably solution in a kind of hydrocarbon solvent.In the disclosure of invention, Lewis acid is meant that any is the compound of electron acceptor(EA).Best activating compounds is the compound that not only can regard Lewis acid as but also can regard metal alkylide as, comprises the mixture of derivative, haloalkyl aluminum compound and the above-claimed cpd of alkylaluminium cpd, alkylaluminium cpd, but is not limited to these.Exemplary compounds comprises triethyl aluminum, diethyl aluminum, tri-chlorination diethyl aluminum and composition thereof, but is not limited to these.Optimum alkylaluminium cpd is a triethyl aluminum, and its catalytic activity is best.

Hydrocarbon solvent can be the lewis acidic hydrocarbon of any energy dissolving.The hydrocarbon that should adopt comprises C _6-50Aromatic substance, but be not limited to these.The most handy toluene is made hydrocarbon solvent, because it is easy to remove and to the interference minimum of synthetic catalyzer.

Use metal alkylide and (or) during the such activating compounds of Lewis acid, any consumption all is so that Chromium pyrrolate catalyst activation and reaction with it.Common every gram chromium can restrain Lewis acids with about 200.Every gram pyrroles should use about 1-100 gram resemble metal alkylide and (or) the such activating compounds of Lewis acid, in order to reach best catalytic activity, preferably every gram Chromium pyrrolate use about 5-30 gram resemble metal alkylide with (or) the such activating compounds of Lewis acid.Yet lewis acidic consumption can be different with the kind of catalyst system therefor carrier.For example, if with silicon-dioxide and (or) when aluminum oxide is made carrier, uses too much activating compounds (can make the catalytic activity reduction as metal alkylide and (or) Lewis acid).But,, use the activating compounds of this same amount (catalytic activity is reduced greatly as metal alkylide and (or) Lewis acid) if when making carrier with aluminate or phosphate.

As previously mentioned, Chromium pyrrolate, support of the catalyst and activating compounds (as metal alkylide and (or) Lewis acid) under the exsiccant inert atmosphere, mix all the time with (or) contact.Any pressure can be adopted during contact, but, normal atmosphere should be adopted for the ease of operation.Any temperature can be adopted during contact, but, room temperature should be adopted for the ease of operation.Must note not destroying the physical integrity of catalyzer of the band carrier of Chromium pyrrolate, support of the catalyst and generation during mixing.This ternary mixture can contact any time, as long as be enough to make chrome catalysts and make its activation.General about 1 minute-1 week of contact is just enough.Should contact about 30 minutes-24 hours, preferably contact is about 1-12 hour.The too short meeting of mixing time makes each component contact not exclusively, can not further improve catalytic effect but mixing time is long.

The method of the catalyzer of another kind of preparation band carrier, it also is a kind of method that should adopt at present, be that one or more solid Chromium pyrrolate compounds of the present invention and foregoing a kind of hydrocarbon solvent (for example toluene) and foregoing a kind of activating compounds (are mixed as a kind of metal alkylide and (or) Lewis acid, for example triethyl aluminum).Under any pressure or temperature this mixture is stirred, churning time will be enough to make the Chromium pyrrolate compound dissolution, and generally this time was about 1 minute-1 week, was preferably 1 hour about-24 hours, preferably was about 3-12 hour.Can adopt envrionment temperature and pressure for the ease of operation.Usually generate brown solution.

Behind the solution thorough mixing, a kind of carrier is added in this solution, and stir, so that solution fully contacts with carrier.The consumption of carrier will be enough to hold the Chromium pyrrolate compound.Generally, disclosed identical in the essential consumption of carrier and the foretype method.Any suitable pressure and temperature can be adopted in the operating process, but envrionment temperature and pressure should be adopted for the ease of operating.Usually mix and (or) be about 30 minutes duration of contact-1 week, be preferably about 3-48 hour, preferably be about 5-24 hour, to reach maximum efficient and to make the carrier of abundant contact.

Solution can be filtered then, reclaim the solid catalysis product.This catalysate, the same with reactant with reaction mixture, should be kept under the inert atmosphere, to keep its chemical stability.

If reclaim chromium cpd (for example Chromium pyrrolate), and will with its effect not with the trimerization of carrier and (or) polymerizing catalyst, can make alkene under one or more even chromium cpds of the present invention, a kind of situation about existing, carry out trimerization or polymerization as the stable hydrocarbon and the Lewis acid of thinner.Also hydrogen can be fed in the reactor with accelerated reaction.

Reactant

Be applicable to that utilizing Catalyst And Method of the present invention to carry out the polymeric reactant is energy polymeric olefinic compound, this is meant that this compound itself can react mutually or can react with other olefinic compounds.Catalyzer of the present invention can be used at least a straight chain or the branched list-1-alkene that contains 2-8 carbon atom approximately of polymerization.Exemplary compounds comprises ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene and composition thereof, but is not limited to these.

The reactant that is applicable to trimerization reaction of the present invention (being the polymerization of any three kinds of alkene) is the olefinic compounds that meets following two conditions: a, self can react, can carry out trimerization and generate useful product, for example ethene self reacts and generates hexene; (or) b, can react with other olefinic compounds, promptly carry out common trimerization and generate useful product, for example ethene and hexene carry out common trimerization and generate decene and (or) 1-tetradecylene, ethene and 1-butylene carry out common trimerization and generate octene, or 1-decene and ethene carry out common trimerization and generate 1-tetradecylene and (or) the 1-docosene." trimerization " used herein this term comprises top said " trimerization altogether ".

Be applicable to that olefinic compounds of the present invention, as to carry out terpolymerization is that those per molecules contain 2-30 carbon atom approximately and have the compound of place's olefinic double bond at least.Typical compound comprises acyclic olefin and cyclenes, the mixture of ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, all four kinds of positive octenes, all four kinds of positive nonenes and any two or more above-claimed cpd for example, but be not limited to these.If with branched alkene and (or) cyclenes makes reactant, although we are reluctant to be bound by theory, we think that still steric hindrance can hinder trimerization reaction.Therefore, the chain portion of alkene and (or) circular part should be away from carbon-to-carbon double bond.

Reaction conditions

Reaction product, promptly trimer and (or) multipolymer, can utilize equipment commonly used and contact method, with contact system of the present invention carry out solution polymerization, slurry polymerization and (or) vapour phase polymerization and making.Any known method makes one or more monomers contact with catalyst system in the available solid catalyst technology.A kind of method easily is that catalyst system is suspended in a kind of organic medium, and stirs the mixture, make catalyst body tie up to trimerization and (or) be in suspended state from start to finish in the polymeric process.Also can adopt other known contact methods, as fluidized-bed, gravitating bed and these methods of fixed bed.Also hydrogen can be fed in the reactor with accelerated reaction.

Catalyst system of the present invention be specially adapted to the slurry trimerization and (or) polymerization.This slurry polymerization generally carries out in a kind of inert diluent (medium), for example carries out in a kind of alkane, cycloalkanes or aromatic hydrocarbons.A kind of typical reaction diluent is a Trimethylmethane.When reactant was mainly ethene, the temperature of employing was about 60-110 ℃.

Product

Olefinic product of the present invention and (or) polymerisate obtained many-sided application, for example preparation homopolymer, multipolymer and (or) during terpolymer as monomer.Polymerisate of the present invention for example polyethylene has obtained to use widely.

Can further understand the present invention and advantage thereof with reference to following embodiment.

Embodiment

Contain the preparation of chromium cpd

The operation of all reactants or in filling the dried case of nitrogen, carry out, or vacuumize or fill nitrogen, carry out in the airfree glassware.Under nitrogen atmosphere, on benzophenone sodium ketyl, distill so that tetrahydrofuran (THF) (THF), toluene, benzene, diethylbenzene (97%1,2-, 1,3-, 1,4-isomer mixture) and pentane are purified, clean the degassing with nitrogen then.Glycol dimethyl ether (DME) (Aldrich, anhydrous) can use after cleaning the degassing with nitrogen, does not need further to purify.Pyrroles's (Aldrich, 98%) carries out earlier vacuum distilling on sodium, clean the degassing with nitrogen then.2,5-dimethyl pyrrole thing is to use the calcium sulfate drying earlier, carries out straight empty distillation then.2, the preparation method of 5-dimethyl pyrrole sodium makes 2, and 5-dimethyl pyrrole thing and excessive sodium (40% (weight) dispersion liquid in the petroleum solvent of about 150-200 ℃ cut) react in the tetrahydrofuran (THF) that refluxes under nitrogen atmosphere.The preparation method of pyrrolesization sodium is that the NaH (Aldrich, 60% (weight) dispersion liquid in mineral oil) or the sodium (40% (weight) dispersion liquid in the petroleum solvent of about 150-200 ℃ cut) that make pyrroles and equimolar amount (1: 1) at room temperature react in glycol dimethyl ether or tetrahydrofuran (THF) (THF) under nitrogen atmosphere.Triethyl aluminum (TEA) (Aldrich1.0M hexane and 1.9M toluene) can promptly use by its state of stocking up.KetjenB grade aluminum oxide (Al ₂O ₃) and Davison952 silicon-dioxide (SiO ₂) be commodity as support of the catalyst.Fluoro-aluminum oxide (F/Al ₂O ₃, 15% (weight) F) and be by with NH ₄HF ₂Make in the methanol solution adding KefjenB grade aluminum oxide.Phosphatization silicon-dioxide (P/SiO ₂, P/Si mol ratio=0.1) and be by with 10%H ₃PO ₄Make in/methanol solution adding Davison952 the silicon-dioxide.Aluminum phosphate (the AlPO that is used for following test ₃) be by people such as McDaniel at United States Patent (USP) the 4th, 364, the preparation of method described in No. 855 (1982).Making carrier activatory method is that the carriers that will be no more than 25 grams place a porous silica tube, and makes its fluidisation and descend calcining 3 hours at 700 ℃ with air, but P/SiO ₂Exception, it is to calcine 3 hours down at 350 ℃.Change airflow into nitrogen gas stream then, till carrier is cooled to envrionment temperature.

The Chromium pyrrolate complex compound is generally made by anhyd chromic chloride (II or III) and pyrrolesization sodium, and its method for making is as follows:

A kind of typical synthetic method that is used to prepare the Chromium pyrrolate complex compound is to make chromium chloride and pyrrolesization sodium (NaC ₄H ₄N or represent with NaPy) in the tetrahydrofuran (THF) (THF) that refluxes, react.1CrCl ₂With the 1 molar reactive thing of the 2NaPy chemistry metering reaction result two kinds of products of emanating out, mainly generate polymeric material-product II, what account for small portion is a kind of five rings complex compound one product I, Cr ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄, see the reaction formula I.

Cr ₅(C ₄H ₄N) ₁₀(C ₄H ₈O) ₄

Five rings complex compound (I) lCrCl ₂Tetrahydrofuran (THF) product I reflux 20 hours+-------------→+reaction formula (1) nitrogen atmosphere polymer complex, then generate dianion square planar complex Cr (NC during the NaPy of (III) 2NaPy product II (mainly) use molar excess ₄H ₄) ₄{ Na} ₂2OC ₄H ₈(product III) and octahedral complex { Cr (C ₄H ₄N) ₅(OC ₄H ₈) { Na} ₂4OC ₄H ₈(product IV) sees reaction formula (2).

{Cr(C ₄H ₄N) ₄}{Na} ₂·2OC ₄H ₈

Square plane Cr (II) CrCl ₂2 hours (major portion) of tetrahydrofuran (THF) product III backflow+-------------→+reaction formula (2) nitrogen atmosphere { Cr (C ₄H ₄N) ₅(OC ₄H ₈) Na) ₂4OC ₄H ₈The octahedra Cr of NaPy (excessive) (III) product IV reaction formula (2) (small part)

The separation method of various products is that the product II is separated by precipitating action, and product I, III, IV are to make its crystallization from THF solution by adding pentane.

Embodiment 1

In order to prepare five rings complex compound product I (Cr ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄) and polymeric material-product II, chromous chloride (2.0 grams/16.27 mmoles) is mixed in tetrahydrofuran (THF) with pyrrolesization sodium (33.68 mmole) and refluxed 20 hours.Reaction mixture is filtered (with the frit of medium porosity), make product I (Cr by adding pentane with gained filtrate ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄) and polymeric material (product II) fractional crystallization.The crystallization of polymeric material elder generation is blue solid, then is Cr ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄Crystallization, for opaque dark blue/purple crystals.

To product I (C ₅₆H ₇₂O ₄N ₁₀Cr ₅) result that analyzes is as follows:

Calculation result C55.62; H6.00; N11.58% (weight)

Measured result C55.46; H6.32; N11.15% (weight)

The analysis measured result of product II is: Cr11.5; C59.75; H7.61; N9.17% (weight), but can change with deposition condition.The X ray crystal structure of product I shows that it is a five rings complex compound, contains acyl ammonia-pyrryl bridged bond, acyl ammonia-pyrryl end group and tetrahydrofuran (THF) ligand (Fig. 1 and 2).

Embodiment 2

In order to prepare (Cr (NC ₄H ₄) ₄{ Na} ₂2OC ₄H ₈(product III) and { Cr (C ₄H ₄N) ₅(OC ₄H ₈) { Na} ₂4OC ₄H ₈(product IV), chromous chloride (3.0 gram/24.4 mmoles) is mixed in tetrahydrofuran (THF) with pyrrolesization sodium (100.9 mmole) and refluxed 2 hours, see reaction formula (2), reaction mixture filtered (with medium porosity frit), and in gained filtrate adding pentane and make { Cr (NC ₄H ₄) ₄{ Na} ₂2OC ₄H ₈(product III) and { Cr (C ₄H ₄N) ₅(OC ₄H ₈) { Na} ₂4OC ₄H ₈(product IV) fractional crystallization.Elder generation's crystalline is the product III, is transparent orange/red crystals, and then crystalline is the product IV, is transparent purple crystals.Though we do not think bound by theory, we think generate the product IV be since in preparation process employed chromous chloride (the Alfa chromous chloride, anhydrous, contain 5-10% (weight) CrCl ₃) in contain chromium chloride.

To C ₂₄H ₃₂N ₄O ₂CrNa ₂The result that (product III) analyzed is

Calculation result C56.94; H6.32; N11.07% (weight)

Measured result C57.04; H6.30; N10.92% (weight)

To C ₄₀H ₆₀N ₅O ₅CrNa ₂The result that (product IV) analyzed is

Calculation result C60.90; H7.67; N8.88% (weight)

Measured result C60.81; H7.74; N9.44% (weight)

The x-ray crystal structure of product III shows that it is one to contain the square planar complex (Fig. 4) of acyl ammonia-pyrryl ligand end group.The x-ray crystal structure of product IV shows that it is one to contain the octahedral complex (Fig. 5 and 6) of acyl ammonia-pyrryl end group and tetrahydrofuran (THF) ligand.

Embodiment 3

By pyrrolesization sodium and CrCl ₃The product that reacts and get is suitable for preparing deactivated catalyst most.Pyrroles's (7.0 milliliters/100.9 mmole) and NaH (60% purity, 4.2 grams, about 105 mmoles) are mixed, in glycol dimethyl ether till bubbling no longer.At ambient temperature chromium chloride (5.33 grams/33.7 mmoles) is added in this solution.Make this reaction mixture under nitrogen atmosphere, reflux 5 minutes (seeing reaction formula 3).

Generate green solution, this solution is filtered (with medium porosity frit) and under vacuum except that desolvating, vacuumize then and made its drying in 12 hours.The Chromium pyrrolate that generates is green solid (a product V).It just is used to prepare active catalyst without being further purified.

Embodiment 4

All single crystals X-ray structure analysis all is by CrystalyticsCompany, Lincoln, and Nebraska finishes.Embodiment 4,5,6 and 9 comprises the analytical data of gained and subsequently by computer-generated data.

Recorded (Cr ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄) the monocrystalline x-ray structure of (product I), as depicted in figs. 1 and 2.About collecting being described below of used monocrystalline sample of data and crystal cup:

Color: dark blue

Shape: rectangular parallelepiped

Size: 0.20 * 0.48 * 0.80 millimeter

Crystal cup: crystal be with epoxy sealing in filling the thin-walled glass kapillary of nitrogen.

Crystalline orientation: make the crystalline longest edge almost parallel with (phi) axle of diffractometer.

The width at half place of ω scanning height: 0-38 °

The data of spacer and structure cell are as follows:

Crystallographic system: three is tiltedly brilliant

Spacer and space-number ²:

(No.2)

The computer center's reflection number (Number of Compnter-Centered Reflections) that is used for the least-squares refinement of unit cell dimension:

1520＞25°℃=20±1°

Lattice parameter and effective standard deviation thereof (esd)

a=10.803(2)????α=85.59(2)°????v=1407.9(6) ³

b=9.825(2)?????β=96.23(2)°????z=1

c=14.212(4)????γ=109.99(2)°??λ=0.71073

Molecular weight: 1209.24 atomic mass units (amu)

Bulk density: 1.427 gram per centimeters ^-1

Linear absorption coefficient: 0.96 millimeter ^-1

Table I _ V has been listed the gained parameter that is used for producing molecular structure illustrated in figures 1 and 2.

Table 1 (Cr ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄) ^a

The atomic coordinate of the non-hydrogen atom in the crystal

Atomic species b	Disperse coordinate			Effective homogeneity thermal parameter B, A 2×10 c
					??10 4X	????10 4Y	??10 4X
	?Cr 1?Cr 2?Cr 3?N 1a?C 1a?C 2a?C 3a?C 4a?N 1b?C 1b?C 2b?C 3b?C 4b?N 1c?C 1c?C 2c?C 3c	??O d??636(1) -1179(1) -1155(3) -2195(4) -3313(4) -3014(4) -1728(4) ?1566(3) ?1753(4) ?3C35(5) ?3736(4) ?2823(4) -320(3) ?375(4) ??29(5) -908(5)	???O d2281(1) ??84(1) ?935(3) ??64(4) ?390(5) 1486(5) 1791(4) 1902(3) 3095(4) 3751(5) 2986+5) 1865(4) 2997(3) 3732(4) 4919(4) 4967(4)					??O/ d1500(1) 3122(1) ?715(2) ?1231(3) ?965(3) ?257(3) ?116(3) ?331(2) -308(3) -432(3) ?131(3) ?587(3) 2480(2) 3732(3) 3383(3) 2631(3)	????25(1) ????24(1) ????28(1) ????25(1) ????31(1) ????41(1) ????43(1) ????34(1) ????29(1) ????36(1) ????51(2) ????51(2) ????38(1) ????27(1) ????34(1) ????43(1) ????42(1)

Table 1 (continuing)

Atomic species b	Disperse coordinate				Effective homogeneity thermal parameter B, A 2×10 c
						?10 4x	10 4y	????10 4x
	?C 4c?N 1d?O 1d?C 2d?C 3d?C 4d?N 1e?O 1e?C 2e?C 3e?C 4e?O 1f?C 1f?C 2f?C 3f	-1105(4) ?443(3) ?1600(4) ?2321(4) ?1567(5) ?422(4) ?-1972(3) ?-t344(5) ?-2189(5) ?-3361(5) ?-3206(5) ?2351(3) ?3536(4) ?4470(6) ?3642(5)	??3809(4) ??350(3) ??715(4) ?-133(5) ?-1070(5) ?-763(4) ?-1122(3) ?-2107(4) ?-3307(4) ?-3061(4) ?-1731(4) ??3985(3) ??4018(4) ??5479(6) ??6408(5)	2101(3) 2743(2) 3289(3) 3102(3) 2403(3) 2203(3) 3801(2) 4069(3) 4503(3) 4531(3) 4097(3) 1883(2) 2483(3) 2336(5) 2147(4)						????32(1) ????28(1) ????36(1) ????46(2) ????46(2) ????36(1) ????35(1) ????41(1) ????44(1) ????47(1) ????47(1) ????32(1) ????43(1) ????76(2) ????62(2)

Table 1 (continuing)

Atomic species b	Disperse coordinate			Effective homogeneity thermal parameter B, A 2×10 c
					??10 4x	??10 4y	?10 4x
	?C 4f?O 1g?C 1g?C 2g?C 3g?C 4g	?2396(4) -2551(3) -3763(4) -4097(5) -3524(5) -2319(5)	5463(4) 1543(3) 1733(5) 2625(6) 2241(6) 1977(6)					1635(3) 3659(2) 3232(3) 3907(4) 4845(3) 4633(3)	????40(1) ????35(1) ????44(1) ????57(2) ????57(2) ????50(2)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1.

C is 1/3 of a quadrature B1j trace of tensor.

This is the value that symmetry requires for d, does not therefore list the estimation standard deviation.

Table 2 (Cr ₅(NC ₄H ₄) ₁₀(OC ₄H ₈) ₄) ^{A, b}The anisotropy thermal parameter of the non-hydrogen atom in the crystal

Atomic species c	Anisotropy thermal parameter ( 6×10)
							?D 11	??D 12	?D 33	????D 12	????D 13	??????D 23
	?Cr 1?Cr 2?Cr 3?N 1a?C 1a?C 2a?C 3a??C 4a??N 1b??C 1b??C 2b??C 3b??C 4b??N 1c	20(1) 23(1) 27(1) 21(1) 28(2) 23(2) 31(2) 36(2) 24(1) 4061) 46(2) 25(2) 29(2) 28(1)	23(1) 22(1) 26(1) 27(1) 31(2) 49(2) 51(2) 32(2) 25(1) 31(2) 42(2) 50(2) 38(2) 25(1)	32(1) 27(1) 34(1) 29(1) 30(2) 49(2) 52(2) 34(2) 35(1) 33(2) 54(2) 71(3) 48(2) 30(1)	????5(1) ????7(1) ???11(1) ????8(1) ????4(1) ????8(2) ???22(2) ???15(1) ???3(1) ???2(1) ??-7(2) ??-3(2) ??10(1) ??11(1)	????5(1) ????3(1) ????8(1) ????1(1) ????8(1) ????5(2) ???-7(2) ???-2(1) ????5(1) ???11(1) ???24(2) ???15(2) ????0(2) ????3(1)							????-4(1) ????-2(1) ?????1(1) ????-2(1) ????-4(1) ???-16(2) ???-11(2) ????-3(1) ????-4(1) ????-1(1) ????-5(2) ???-27(2) ???-15(2) ????-2(1)

Table 2 (continuing)

Atomic species c	Anisotropy thermal parameter ( 6×10)
							????B 11	????B 22	????B 33	????B 12	?B 13	????B 23
	????C 1c????C 2c????C 3c????C 4c????N 1d????C 1d????C 2d????C 3d????C 4d????N 1e????C 1e????C 2e????C 3e????C 4e????O 1f????C 1f????C 2f	????36(2) ????52(2) ????51(2) ????35(2) ????32(1) ????33(2) ????36(2) ????61(3) ????49(2) ????36(2) ????46(2) ????64(3) ????55(3) ????39(2) ????29(1) ????34(2) ????45(3)	????35(2) ????34(2 ????31(2) ????34(2) ????23(1) ????32(2) ????50(2) ????44(2) ????35(2) ????30(1) ????36(2) ????30(2) ????31(2) ????38(2) ????25(1) ????44(2) ????67(3)	????31(2) ????43(2) ????50(2) ????31(2) ????31(1) ????42(2) ????59(2) ????47(2) ????31(2) ????42(2) ????46(2) ????37(2) ????46(2) ????62(2) ????40(1) ????45(2) ????95(4)	????10(1) ????13(2) ????22(2) ????16(1) ????12(1) ?????9(1) ????24(2) ????36(2) ????23(2) ????13(1) ????20(2) ????15(2) ????-1(2) ????9(2) ????6(1) ????9(2) ???-3(2)	?????4(1) ?????6(2) ?????5(2) ?????4(1) ?????6(1) ?????6(2) ?????6(2) ????11(2) ?????4(2) ????14(1) ????10(2) ?????7(2) ????18(2) ????17(2) ????-1(1) ????-8(2) ???-15(3)							???-3(1) ???-13(1) ????-5(2) ????1(1) ????3(1) ???-O(1) ???11(2) ????3(2) ????1(1) ????4(1) ????6(2) ????4(1) ????-O(2) ????4(2) ????-2(1) ????-6(2) ????-6(3)

Table 2 (continuing)

Atomic species b	Anisotropy thermal parameter ( 6×10)
							????B 11	????B 22	????B 33	????B 12	????B 13	?????B 23
	????C 3f????C 4f????O 1g????C 1g????C 2g????C 3g????C 4g	????59(3) ????45(2) ????34(1) ????31(2) ????47(3) ????60(3) ????45(2)	????34(2) ????23(1) ????41(1) ????56(2) ????65(3) ????75(3) ????77(3)	????78(3) ????48(2) ????37(1) ????50(2) ????72(3) ????50(2) ????35(2)	????-2(2) ?????7(1) ????19(1) ????20(2) ????35(2) ????36(2) ????27(2)	???-6(3) ????6(2) ????7(1) ????4(2) ????2(2) ???16(2) ????8(2)							????-9(2) ????-1(1) ????-1(1) ????-5(2) ???-12(2) ????-8(2) ????-5(2)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The form of b anisotropy thermal parameter sees that structure reports the note 8 on the 6th page.

The mark of c atom is consistent with Fig. 1.

Table 3Cr ₅(NC ₄H ₄) ₁₀(OC ₄N ₈) ₄ ^aHydrogen atom coordinate in the crystal

Atomic species b	Divide coordinate
				????10 4x	????10 4y	????10 4z
	?H 1a?H 2a?H 3a?H 4a?H 1b?H 2b?H 3b?H 4b?H 1c?H 2c?H 3c?H 4c?H 1d?H 2d?H 3d?H 4d	???-2129 ???-4154 ???-3608 ???-1267 ????1053 ????3405 ????4676 ????3031 ????1013 ????364 ???-1331 ???-1704 ????1881 ????3177 ????1807 ????-291	????-661 ?????-55 ????1937 ????2506 ????3405 ????4593 ????3202 ????1158 ????3445 ????5592 ????5685 ????3580 ????1460 ?????-88 ???-1790 ???-1252				????1707 ????1219 ????-69 ????-339 ????-617 ????-834 ?????189 ????1020 ????3687 ????3881 ????2512 ????1540 ????3743 ????3396 ????2120 ????1752

Table 3 (continuing)

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4z
	????H 1e????H 2e????H 3e????H 4e????H 1fa????H 1fb????H 2fa????H 2fb????H 3fa????H 3fb????H 4fa????H 4fb????H 1gz????H 1gb????H 2gz	???-446 ???-1997 ???-4139 ???-3878 ????3351 ????3882 ????5068 ????4965 ????3462 ????4068 ????2417 ????1641 ???-3631 ???-4455 ???-5037	????-1976 ????-4161 ????-3699 ????-1286 ?????3836 ?????3308 ?????5771 ?????5524 ?????6711 ?????7245 ?????5653 ?????5625 ?????2231 ??????813 ?????2381				????3968 ????4742 ????4803 ????4012 ????3136 ????2299 ????2893 ????1806 ????2728 ????1757 ?????964 ????1639 ????2623 ????3162 ????3901

Table 3 (continuing)

Atomic species b	Fractional coordinates
				??10 4x	?10 4y	????10 4z
	?H 2gb?H 3ga?H 3gb?H 4gz?H 4gb	-3704 -4129 -3307 -2173 -1565	?3640 ?1385 ?3025 ?1220 ?2846				????3750 ????5124 ????5266 ????5050 ????4703

The a hydrogen atom (suppose carbon atom generation as " taking " on its corresponding carbon atom

SP ²Or SP ³-hydridization and c h bond length are 0.96 ) comprise

In the calculating of textural factor.The isotropy thermal parameter of each hydrogen atom is fixing

Be its covalent linkage effective homogeneity thermal parameter of bonded carbon atom with it

1.2 doubly.The b hydrogen atom uses numeric suffix identical with its carbon atom and literal subscript to mark, but

Also other ties with same carbon atom in addition with the district power one literal subscript (a or b) when needing

Each hydrogen atom that closes

Table 4Cr ₅(NC ₄H ₄) ₁₀(OC ₄N ₈) ₄ ⁸The bond distance of the non-hydrogen atom in the crystal

Kind b	Bond distance A	Kind b	Bond distance A
				?Cr 1…Cr 2?Cr 2…Cr 3?Cr 1-N 1a?Cr 1-N 1b?Cr 2-N 1a?Cr 2-N 1b?Cr 2-N 1c?Cr 3-N 1c?Cr 3-N 1d?Cr 3-N 1e?Cr 2-O 1f?Cr 3-O 1g	3.066(1) 3.121(1) 2.153(3) 2.92(3) 2.178(3) 2.149(3) 2.112(4) 2.172(3) 2.101(4) 2.037(3) 2.082(2) 2.068(3)	????O 1f-C 1f????O 1f-C 4f????O 1g-C 1g????O 1g-C 4g????C 1a-C 2a????C 2a-C 3a????C 3a-C 4a????C 1b-C 2b????C 2b-C 3b????C 3b-C 4b????C 1c-C 2c????C 2c-C 3c????C 3c-C 4c	????1.451(5) ????1.453(5) ????1.448(6) ????1.451(5) ????1.360(6) ????1.395(6) ????1.351(6) ????1.338(6) ????1.393(7) ????1.376(6) ????1.365(7) ????1.400(6) ????1.356(6)

Table 4 (continuing)

Kind b	Bond distance A	Kind b	Bond distance A
				?N 1a-C 1a?N 1a-C 4a?N 1b-C 1b?N 1b-C 4b?N 1c-C 1c?N 1c-C 4c?N 1d-C 1d?N 1d-C 4d?N 1e-C 1e?N 1e-C 4e	1.399(4) 1.397(5) 1.398(5) 1.379(6) 1.388(4) 1.394(6) 1.349(5) 1.377(5) 1.370(6) 1.361(6)	?C 1d-C 2d?C 2d-C 3d?C 3d-C 4d?C 1e-C 2e?C 2e-C 3e?C 3e-C 4e?C 1f-C 2f?C 2f-C 3f?C 3f-C 4f?C 1g-C 2g?C 2g-C 3g?C 3g-C 4g	1.376(7) 1.396(6) 1.367(8) 1.370(5) 1.374(8) 1.366(6) 1.460(6) 1.474(9) 1.496(6) 1.496(8) 1.485(7) 1.476(9)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1.

Table 5Cr ₅(NC ₄N ₄) ₁₀(OC ₄N ₈) ₄ ^aThe bond angle of the non-hydrogen atom in the crystal

Kind a	The bond angle degree	Kind b	The bond angle degree
				????N 1aCr 1N 1b????N 1aCr 1N 1a′c ????N 1bCr 1N 1a′c ????N 1bCr 1N 1b′c ????N 1aCr 2N 1b????N 1aCr 2N 1c????N 1bCr 2N 1c????N 1aCr 2O 1f????N 1bCr 2O 1f????N 1cCr 2O 1f????N 1cCr 3N 1d????N 1cCr 3N 1e	????84.8(1) ????180.0(-) d????95.2(1) ????180.0(-) d????82.9(1) ????96.5(1) ????168.9(1) ????162.4(1) ????89.5(1) ????87.9(1) ????88.1(1) ????176.5(1)	????Cr 1N 1aCr 2????Cr 1N 1aC 1a????Cr 2N 1aC 1a????Cr 1N 1aC 4a????Cr 2N 1aC 4a????C 1aN 1aC 4a????Cr 1N 1bCr 2????Cr 1N 1bC 1b????Cr 2N 1bC 1b????Cr 1N 1bC 4b????Cr 2N 1bC 4b????C 1bN 1bC 4b????Cr 2N 1cCr 3????Cr 2N 1cC 1c	????90.2(1) ????121.2(2) ????118.0(2) ????113.4(2) ????110.6(2) ????103.5(3) ????92.6(1) ????117.9(2) ????107.6(3) ????120.6(3) ????113.0(3) ????104.％(3) ????93.5(1) ????121.4(3)

Table 5 (continuing)

Kind b	The bond angle degree	Kind b	The bond angle degree
				?N 1dCr 3N 1e?N 1cCr 3O 1g?N 1dCr 3O 1g?N 1aCr 3O 1g?N 1aC 1aC 2a?C 1aC 2aC 3a?C 2aC 3aC 4a?C 3aC 4aN 1a?N 1bC 1bC 2b?C 1bC 2bC 3b?C 2bC 3bC 4b?C 3bC 4bN 1b?N 1cC 1cC 3c?C 1cC 2cC 3c?C 2cC 3cC 4c	????93.5(1) ????88.8(1) ????170.4(1) ????89.1(1) ????110.6(3) ????107.5(4) ????106.9(4) ????111.5(3) ????111.2(4) ????107.4(4) ????107.0(4) ????110.1(4) ????110.9(4) ????106.8(4) ????107.2(4)	?Cr 3N 1cC 1c?Cr 2N 1cC 4c?Cr 3N 1cC 4c?C 1cN 1cC 4c?Cr 3N 1dC 1d?Cr 3N 1dC 4d?C 1dN 1dC 4d?Cr 3N 1eC 1e?Cr 3N 1eC 4e?C 1eN 1eC 4e?Cr 2O 1fC 1f?Cr 2O 1fC 4f?C 1fO 1fC 4f?Cr 3O 1gC 1g?Cr 3O 1gC 4g	100.0(2) 116.1(2) 121.5(2) 104.2(3) 121.3(3) 127.8(3) 106.4(4) 126.3(3) 128.3(3) 105.3(3) 131.5(2) 118.9(2) 109.1(3) 131.9(3) 118.6(3)

Table 5 (continuing)

Kind b	The bond angle degree	Kind b	The bond angle degree
				?C 3cC 4cN 1c?N 1dC 1dC 2d?C 1dC 2dC 3d?C 2dC 3dC 4d?C 3dC 4dN 1d?N 1eC 1eC 2e?C 1eC 2eC 3e?C 2eC 3eC 4e?C 3eC 4eN 1e	110.9(3) 110.3(4) 106.7(4) 106.6(5) 109.9(3) 110.0(4) 107.2(4) 106.7(4) 110.8(5)	?C 1gO 1gC 4g?O 1fC 1fC 2f?C 1fC 2fC 3f?C 2fC 3fC 4f?C 3fC 4fO 1f?O 1gC 1gC 2g?C 1gC 2gC 3g?C 2gC 3gC 4g?C 3gC 4gO 1g	109.5(4) 105.0(4) 104.9(4) 104.4(4) 105.4(4) 104.8(4) 104.2(5) 104.2(4) 106.1(4)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.The mark of b atom is consistent with Fig. 1.The atom of c band (') mark has-X with the atom with (') number not ,-Y, and the relation of-Z fractional coordinates symmetry action, (this is the value that symmetry requires to fractional coordinates Z) to see Table 1d, therefore unlisted estimation standard deviation for X, Y.

Embodiment 5

Figure 3 shows that Cr (NC ₄H ₄) ₄The part of-product III-the monocrystalline x-ray structure.Figure 4 shows that (Na) ₂(Cr (NC ₄H ₄) ₄) 2 (OC ₄H ₈)-product III-the monocrystalline x-ray structure.About collecting being described below of used monocrystalline sample of data and crystal cup:

Color: red-orange

Shape: rectangular parallelepiped

Size: 0.50 * 0.55 * 0.65 millimeter

Crystal cup: crystal is bonded on the thin-walled glass inwall capillaceous, and nitrogen-filled seal.

Crystalline orientation: make the crystalline longest edge almost parallel with the axle of diffractometer.

ω scanning height one is full of the width at place: 0.86 °

The data of spacer and structure cell are as follows:

Crystallographic system: oblique crystal

Spacer and space-number ²: C2/C-C _2b(No.15)

The computer center's reflection number that is used for the least-squares refinement of unit cell dimension:

15??20＞25°℃=20+1°

Lattice parameter and effective standard deviation thereof:

a=9.522(2)?????α=90.0c°????V=2697(1) ³

b=15.118(2)????β=98.99(1)°?Z=4

c=18.967(3)????γ=90.00°????λ=0.71073

Molecular weight: 506.52 atomic mass units

Bulk density: 1.248 gram per centimeters ³

Linear absorption coefficient: 0.47 millimeter ^-1

Table VI-X has been listed the gained parameter that is used for producing Fig. 3 and molecular structure shown in Figure 4.

Table 6 (Na) ₂(Cr (NC ₄H ₄) ₄)-2OC ₄E ₈ ^aThe atomic coordinate of the non-hydrogen atom in the crystal

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					????10 4x	????10 4y	????10 4z
	Negatively charged ion
????Cr ????N 1????N 2????N 3????C 11????C 12????C 13????C 14????C 21????C 22????C 31????C 32						????8 d????1981(4) ????8 d????8 d????3241(5) ????4224(6) ????3513(7) ????2894(7) ????987(5) ????582(4) ????398(5) ????236(7)	2982(1) 2924(2) 4343(3) 1612(3) 2958(3) 2768(3) 2638(4) 2734(4) 4884(3) 5753(3) 1891(3) ?213(3)	????2588 d????3183(2) ????2588 d????2588 d????3888(3) ????3587(3) ????4146(3) ????3884(3) ????2926(3) ????2766(3) ????1996(4) ????2189(5)	????58(1) ????56(1) ????52(1) ????78(2) ????65(2) ????73(2) ????82(2) ????76(2) ????68(1) ????69(2) ????94(2) ????133(6)

Table 6 (continuing)

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					????10 4x	????10 4y	????10 4z
	Positively charged ion
????Na					????2381(2)	6879(1)	????1783(1)		????69(1)
	The crystallization solvent
????O 1????C 41????C 42????C 43????C 44						2865(4) 2759(11) 2884(11) 1893(18) 1699(9)	5188(2) 5174(5) 4319(5) 3786(5) 4231(4)	????838(2) ????239(4) ????-79(4) ????264(5) ????982(4)	????83(1) ????143(4) ????148(4) ????142(4) ????128(3)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1 and 2.

C is 1/3 of a Bij trace of tensor.

This is the value that symmetry requires for d, does not therefore list the estimation standard deviation.

Table 7 (Na) ₂(Cr (NC ₄H ₄) ₄)-2OC ₄H ₈ ^A.bThe anisotropy thermal parameter of the non-hydrogen atom in the crystal

Atomic species b	Anisotropy thermal parameter (A 2×10)
							????B 11	????B 22	????B 33	????B 12	??B 13	??B 23
	Negatively charged ion
?Cr ?N 1?N 2?N 3?C 11?C 12?C 13?C 14?C 21?C 22?C 31?C 32								64(1) 69(2) 64(3) 65(3) 79(3) 78(3) 183(4) ?86(3) ?66(2) ?68(3) ?65(3) ?71(5)	????34(1) ????44(2) ????39(2) ????38(2) ????58(2) ????62(3) ????79(3) ????86(3) ????45(2) ????38(2) ????61(3) ????46(2)	??55(1) ??56(2) ??56(3) ?187(4) ??78(3) ??84(3) ??58(3) ??58(3) ??78(3) ?185(4) ?152(5) ?266(15)	????8 d??6(1) ????8 d????8 d??-6(2) ???4(2) ??22(3) ??16(3) ??-2(2) ??-7(2) ???6(2) ???6(3)	?15(1) ?12(1) ?16(2) ?14(3) ?18(2) ??7(2) ?-8(3) ?16(2) ?15(2) ?27(2) ??9(3) -28(6)	???8 d?6(1) ???8 d???8 d??2(2) ?-8(2) ??8(2) ??5(2) ?-6(2) ?-9(2) -36(3) -44(4)

Table 7 (continuing)

Atomic species b	????(A 2* 10) anisotropy thermal parameter
							?B 11	?B 22	B 33	B 12	????B 13	????B 23
	Positively charged ion
Na								?78(1)	?57(1)	81(1)	-2(1)	????15(1)	????-15(1)
	The crystallization solvent
?O 1?C 41?C 42?C 43?C 44								?188(2) ?222(8) ?192(8) ?147(6) ?177(6)	?65(2) 112(5) 168(8) 189(6) ?77(4)	82(2) 116(5) 187(5) 177(8) 124(5)	-18(2) -46(5) ?12(6) -27(5) -21(4)	????38(2) ????92(6) ????78(5) ????48(6) ????76(5)	????-16(2) ????-22(4) ????-32(5) ????-69(6) ????-14(3)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The form of b anisotropy thermal parameter sees that structure reports the note 8 on the 6th page.

The mark of c original text is consistent with Fig. 1 and 2.

This is symmetrical desired value for d, does not therefore list the estimation standard deviation.

Table 8 (Na) ₂(Cr ( ₄H ₄) ₄)-2OC ₄H ₈The atomic coordinate of the hydrogen atom in the crystal

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4z
	Negatively charged ion
H 11H 12H 13H 14H 21H 22H 31H 32					????3456 ????5235 ????3922 ????1341 ????1665 ????1871 ????786 ????483	????3881 ????2748 ????2488 ????2679 ????4687 ????6262 ????1274 ????-381	????2541 ????3688 ????4628 ????4164 ????3285 ????2985 ????1565 ????1937
	The crystallization solvent
H 41aH 43bH 42a					????2258 ????3718 ????3756	????5576 ????5388 ????4891	????-188 ????385 ????-1

Table 8

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4z
	????H 42b????H 43a????H 43b????H 44a????H 44b	????2464 ????995 ????2326 ????2295 ????723	????4348 ????3787 ????3228 ????3973 ????4191				????-583 ????-39 ????377 ????1384 ????969

(vacation there is not carbon atom to produce SP to a hydrogen atom as " taking " desirable atom on its corresponding carbon atom ³-change and c h bond is long is 0.96A) each tropism's thermal parameter of being included in each hydrogen atom in the meter mark of textural factor is fixed, for its with covalent linkage 1.2 times of effective homogeneity thermal parameter of bonded carbon atom with it.The bonded carbon atom is identical with it with covalent linkage with it for the rare subscript of the number of b hydrogen atom, combines hydrogen atom with same carbon atom but also add a literal subscript (a or b) when needing in addition in addition with the district.

Table 9 relates to (Na) ₂(Cr (NC ₄H ₄) ₄)-2OC ₄H ₈ ^aThe negatively charged ion bond distance and the bond angle of non-hydrogen atom in the crystal

Kind b	Bond distance A	Kind b	Bond distance A
				????Cr-N 1????Cr-N 2????Cr-N 3????N 1-C 11????N 1-C 14????N 2-C 21????N 3-C 31	????2.057(3) ????2.056(4) ????2.072(5) ????1.369(7) ????1.344(6) ????1.360(5) ????1.344(7)	????C 11-C 12????C 12-C 13????C 13-C 14????C 21-C 22????C 22-C 22′c ????C 31-C 32????C 32-C 32′c	????1.355(7) ????1.361(9) ????1.374(9) ????1.372(6) ????1.379(9) ????1.376(7) ????1.327(18)
Kind b	The bond angle degree	Kind b	The bond angle degree
				????N 1CrN 2????N 1CrN 3????N 1CrN 1′c ????N 2CrN 3????CrN 1C 11	????92.5(1) ????87.5(1) ????175.1(2) ????180.0(-) d????127.5(3)	????N 1C 11C 12????C 11C 12C 13????C 12C 13C 14????N 1C 14C 13????N 2C 21C 22????C 21C 22C 22′c	????110.5(5) ????107.3(5) ????106.4(5) ????110.9(5) ????110.2(4) ????106.8(3)

Table 9 (continuing)

Kind b	Bond distance A	Kind b	Bond distance A
				?CrN 1C 14?C 11N 1C 14?CrN 2C 21?C 21N 2C 21′c ?CrN 3C 31-?C 31N 3C 31′c	127.1(4) 104.9(4) 127.0(2) 106.0(5) 126.7(3) 106.7(6)	?N 3C 31C 32?C 31C 32C 32′c	109.1(6) 107.5(5)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1.

The atom of c band apostrophe (') mark has with the atom with apostrophe not-x ,-y ,-

The relation of z symmetry action.

Table 10 relates to (Na) ₂(Cr (NC ₄H ₄) ₄)-2OC ₄H ₈ ^aIn positively charged ion and the bond distance and the bond angle of the non-hydrogen atom of recrystallisation solvent

Kind b	Bond distance A	Kind b	Bond distance A
				????Na-O 1????Na…N 1″ c????Na…N 3″ c	2.313(4) 2.888(4) 2.830(4)	????O 1-C 41????O 1-C 44????C 41-C 42????C 42-C 43????C 43-C 44	????1.390(10) ????1.382(7) ????1.43(1) ????1.42(1) ????1.42(1)
Kind b	The bond angle degree	Kind b	The bond angle degree
				????O 1NaN 1″ c????O 1NaN 3″ c	128.6(3) 121.8(3)	????C 41O 1C 44	????107.9(5)

Table 10 (continuing)

Kind b	The bond angle degree	Kind b	The bond angle degree
				????N 1″NaM 3″ c????NaO 1C 41????NaO 1C 44	????59.9(3) ????125.7(4) ????121.8(4)	????O 1C 41C 42????C 41C 42C 43????C 42C 43C 44????O 1C 44C 43	????109.0(7) ????105.0(8) ????107.0(7) ????107.6(7)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.The mark of b atom is consistent with Fig. 2.The two apostrophes (" of c band) atom of mark has-x with the atom with apostrophe not ,-y ,-

The relation of 2 symmetry actions.

The embodiment VI

Figure 5 shows that (Cr (NC ₄H ₄) ₅(OC ₄H ₈)) monocrystalline X-ray structure, Figure 6 shows that (Cr (NC ₄H ₄) ₅(OC ₄H ₈)) (Na) ₂4 (OC ₄H ₈)-product IV-penetrating property of monocrystalline X-structure.About collecting being described below of used monocrystalline sample of data and crystal cup:

Color: purple

Shape: rectangular parallelepiped

Size: 0.50 * 0.55 * 0.63 millimeter

Crystal cup: crystal is bonded on the thin-walled glass inwall capillaceous, and nitrogen-filled seal.

Crystalline orientation: make the crystalline longest edge almost parallel with the phi axle of diffractometer.

The width at half place of ω scanning height: 0.42 °

The data of spacer and structure cell are as follows:

Crystallographic system: oblique crystal

Spacer and space-number ²: P2 ₁-C2 (No.4)

The computer center's reflection number that is used for the least-squares refinement of unit cell dimension:

1520＞20°℃=20+1°

Lattice parameter and effective standard deviation thereof:

a=10.042(2)?α=90.00°????v=2162(1) ³

b=17.242(4)?β=106.54(2)°z=2

c=13.025(3)?γ=90.00°????λ=0.71073

Molecular weight: 788.93 atomic mass units

Bulk density: 1.212 gram per centimeters ³

Linear absorption coefficient: 0.32 millimeter ^-1

Table XI-X V has been listed the gained parameter that is used for producing the molecular structure shown in Fig. 5 and 6.

Table 11 (Cr (NC ₄N ₄) ₅(OC ₄H ₈) (Na) ₂-4OC ₄H ₈ ^aThe atomic coordinate of the non-hydrogen atom in the crystal

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					????10 4x	????10 4y	????10 4z
	Negatively charged ion
????Cr ????N 1a????C 1a????C 2a????C 3a????C 4a????N 1b????C 1b????C 2b????C 3b????C 4b????N 1c						????198(1) ????1694(5) ????1749(7) ????2929(8) ????3661(7) ????2899(6) ????1651(5) ????1463(8) ????2572(9) ????3554(8) ????2952(6) ???-1326(5)	1477 2026(3) 2782(4) 2926(5) 2236(5) 1695(5) 1067(3) ?560(4) ?518(6) 1064(6) 1382(5) 1888(3)	2531(1) 2028(4) 1742(6) 1420(7) 1554(6) 1913(5) 3885(4) 4575(5) 5423(8) 5275(6) 4340(5) 1250(4)	????32(1) ????40(2) ????48(2) ????66(3) ????62(3) ????52(2) ????40(2) ????48(2) ????82(4) ????70(3) ????48(2) ????38(2)

Table 11 (continuing)

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					????10 4x	????10 4y	????10 4z
	?C 1c?C 2c?C 3c?C 4c?N 1d?C 1d?C 2d?C 3d?C 4d?N 1e?C 1e?C 2e?C 3e?C ?O 1f	????-1200(8) ????-2458(8) ????-3435(8) ????-2710(7) ????-32(5) ????504(7) ????107(9) ????-698(8) ????-769(7) ????315(5) ????-574(8) ????-197(10) ????990(10) ????1265(8) ????1356(4)	2172(4) 2270(5) 2038(6) 1826(5) 2455(4) 2562(5) 3278(5) 3629(5) 3108(4) ?505(4) ?277(5) -432(5) -662(6) ?-92(4) ?926(3)					????266(6) ????-476(6) ??????56(7) ????1091(6) ????3445(5) ????4505(6) ????4774(8) ????3832(6) ????3055(6) ????1690(4) ?????704(6) ?????403(7) ????1256(8) ????2016(7) ????3083(4)	????51(2) ????58(3) ????75(3) ????56(3) ????43(2) ????49(2) ????72(3) ????59(3) ????52(2) ????40(2) ????55(3) ????67(3) ????79(4) ????51(3) ????43(1)

Table 11 (continuing)

Atomic species b	Fractional coordinates			Each tropism's thermal parameter of equivalence
					????10 4x	????10 4y	????10 4z
	????C 1f????C 2f????C 3f????C 4f	????-2047(7) ????-3263(10) ????-2833(11) ????-1903(8)	????1244(3) ????713(6) ????-21(6) ????171(5)					????3083(4) ????3706(9) ????3402(8) ????2724(7)	????43(3) ????98(5) ????93(4) ????64(3)
Positively charged ion 1
					????Na 1	????2254(3)	????3336(2)	????3737(3)	????75(1)
Positively charged ion 2
					????Na 2	????1430(3)	????974(2)	????126(2)	????62(1)
The crystallization solvent molecule
					????O 1g????C 1g????C 2g????C 3g????C 4g????C 1h????C 1h????C 2h????C 3h????C 4h	????4576(6) ????5748(9) ????6723(12) ????6503(15) ????5037(14) ????2342(7) ????1316(11) ????2017(16) ????3180(12) ????3551(13)	????3329(4) ????3100(10) ????2831(11) ????3272(11) ????3498(11) ????4602(4) ????5151(7) ????5830(9) ????5561(10) ????4848(7)	????4706(5) ????4433(9) ????5281(9) ????6146(11) ????5737(10) ????3279(6) ????2894(10) ????2541(11) ????2425(10) ????3070(11)	????83(2) ????125(6) ????145(7) ????204(8) ????170(8) ????97(3) ????112(5) ????153(7) ????131(6) ????115(6)

Table 11 (continuing)

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					??????10 4x	?????10 4y	????10 4z
	????O 1i????C 1i????C 2i????C 3i????C 4i????O 1j????C 1j????C 2j????C 3j????C 4j	?????1391(7) ????2235(19) ????2716(17) ????1991(28) ????1010(16) ?????3037(5) ????4389(10) ????4998(16) ????4001(11) ????2728(11)	?????1752(4) ????1594(11) ????2287(14) ????2906(11) ?????2533(7) ??????155(4) ???????48(7) ????-571(10) ?????-840(8) ?????-493(7)					-1377(4) -1998(13) -2337(15) -1934(14) ?-1523(9) ??-264(5) ???427(9) ??-23(16) -1006(10) ??-974(8)	?????80(2) ????160(8) ???165(10) ???204(12) ????128(6) ?????72(2) ????113(5) ????174(8) ????127(6) ?????92(4)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1 and 2.

C is 1/3 of a Bij trace of tensor.

Table 12 (Cr (NC ₄H ₄) ₅(OC ₄H ₈)) (Na) ₂-40C ₄H ₈ ^{A, b}The anisotropy thermal parameter of the non-hydrogen atom in the crystal

Atomic species b	The anisotropy thermal parameter
							????B 11	????B 22	????B 33	????B 12	????B 13	??????B 23
	Negatively charged ion
????Cr ????N 1a????C 1a????C 2a????C 3a????C 4a????N 1b????C 1b????C 2b????C 3b????C 4b????N 1c????C 1c????C 2c????C 3c????C 4c								????29(1) ????33(2) ????48(4) ????55(4) ????37(3) ????40(3) ????36(2) ????52(4) ????73(5) ????51(4) ????41(3) ????33(2) ????52(4) ????64(5) ????32(3) ????42(3)	????31(1) ????44(3) ????37(3) ????61(5) ????82(6) ????64(5) ????44(3) ????51(4) ????85(6) ????88(6) ????55(4) ????41(3) ????51(4) ????62(5) ????92(6) ????78(5)	????38(1) ????44(3) ????59(4) ????90(5) ????76(5) ????52(4) ????36(3) ????40(3) ????83(6) ????54(4) ????45(3) ????39(3) ????51(4) ????37(4) ????89(6) ????48(4)	????1(1) ???-1(2) ???-0(3) ??-19(4) ???-9(3) ????4(3) ????7(2) ???-1(3) ????2(5) ????0(4) ????0(3) ????4(2) ????6(3) ???-1(4) ????4(4) ???-1(3)	????12(1) ????11(2) ????15(3) ????34(4) ????33(3) ????16(3) ?????5(2) ?????9(3) ????13(4) ???-13(3) ?????5(2) ?????9(2) ????16(3) ????-4(3) ????-3(4) ?????9(3)	?????1(1) ?????5(2) ?????3(3) ????13(4) ?????2(4) ????-5(3) ????12(2) ????10(3) ????44(5) ????12(4) ?????4(4) ?????1(2) ?????5(3) ?????4(4) ????29(5) ????14(4)

Table 12 (continuing)

Atomic species b	Anisotropy thermal parameter (A 2×10)
							????B 11	B 22	????B 33	?B 12	?B 13	????B 23
	?N 1d?C 1d?C 2d?C 3d?C 4d?N 1e?C 1e?C 2e?C 3e?C 4e?O 1f?C 1f?C 2f?C 3f?C 4f	????31(2) ????44(3) ????63(4) ????69(4) ????42(3) ????47(3) ????59(4) ????92(5) ????91(6) ????62(4) ????40(2) ????61(4) ????81(6) ???109(7) ????61(4)	44(3) 60(5) 70(6) 43(4) 53(4) 36(3) 49(4) 48(4) 45(5) 23(3) 42(2) 64(4) 95(7) 80(6) 53(4)	56(3) 39(4) 84(6) 73(5) 63(4) 39(3) 53(4) 69(5) 106(7) ?69(5) ?51(2) ?60(4) 144(8) 117(7) ?85(5)	?4(2) -5(3) -11(4) ?9(3) ?8(3) -3(2) -15(3) -20(4) ??4(4) ??7(3) ?-4(2) ?-2(3) ?-24(5) ?-26+5) ?-27(4)	13(2) ?8(3) 20(4) 32(4) 17(3) 17(2) 11(3) 36(4) 37(5) 20(4) 20(2) 39(3) 74(6) 75(6) 30(4)							????-1(3) ???-11(3) ???-47(5) ???-14(4) ?????3(4) ????-7(2) ????-1(4) ???-26(4) ???-13(5) ????-7(3) ?????2(2) ?????4(4) ?????1(6) ????-3(6) ???-16(4)

Table 12 (continuing)

Atomic species b	Anisotropy thermal parameter (A 2×10)
							???B 11	???B 22	????B 33	???B 12	???B 13	????B 23
	Positively charged ion 1
?Na 1?Na 2								????57(2) ????68(2)	???71(2) ???69(2)	95 (2) positively charged ions 2 56 (2)	??-13(1) ???-2(1)	????21(2) ????30(1)	????-2(2) ????-3(2)
	The recrystallisation solvent molecule
?O 1g?C 1g?C 2g?C 3g?C 4g?O 1h?C 1h?C 2h?C 3h?C 4h?O 1i								????58(3) ????54(5) ????96(7) ??129(10) ??134(10) ????71(4) ????92(7) ??212(14) ????99(8) ????99(8) ????98(4)	??95(4) 215(14) 226(15) 277(19) 250(18) ??68(4) ??95(8) ?108(9) 175(14) ??79(7) ??82(4)	??92(4) ?108(8) ?121(9) 148(11) 128(10) ?152(6) ?144(9) 140(10) ?101(8) 168(11) ??73(3)	???-8(3) ????0(7) ???52(9) ??52(12) ??44(11) ???-8(3) ???-2(6) ??36(10) ???-6(9) ??-13(6) ????8(3)	????15(3) ????29(5) ????43(7) ???-56(9) ????39(9) ????32(4) ????28(7) ???50(10) ????-2(6) ????38(8) ????47(3)	????-2(4) ????-7(9) ???51(10) ?-134(13) ??-89(11) ????-3(4) ????-3(7) ????66(9) ????32(9) ????29(8) ????13(3)

Table 12 (continuing)

Atomic species b	Anisotropy thermal parameter (A 2×10)
							??????B 11	????????B 22	???B 33	??????B 12	????B 13	??B 23
	????C 1i????C 2i????C 3i????C 4i????O 1j????C 1j????C 2j????C 3j????C 4j	??230(15) ??112(10) ??370(26) ??223(13) ????59(3) ????88(7) ????94(8) ????83(7) ????82(6)	????128(11) ????222(21) ????124(12) ??????81(7) ??????64(3) ?????101(8) ????190(14) ????130(10) ?????104(8)	168(12) 156(15) 135(12) ?106(8) ??94(4) ?133(9) 205(13) 160(10) ??92(7)	????8(11) ?????1(12) ???-93(15) ?????32(8) ??????5(3) ?????19(6) ????73(10) ????16(7) ????-7(6)	???131(12) ????28(10) ????99(15) ????91(9) ????22(3) ?????2(6) ???-11(9) ????20(7) ????29(5)							?74(10) ?23(16) ?34(10) ??31(6) ?-21(3) ?-58(7) -90(13) ?-86(9) ?-41(6)

Numeral in a parenthesis is the standard error estimate of last position effective digital

The form of b anisotropy thermal parameter is seen the note 8 on 6 pages of the structure report mat woven of fine bamboo strips

The mark of c atom is consistent with Fig. 1 and 2

Table 13 (Cr (NC ₄N ₄) ₉(OC ₄N ₈)) (Nal ₂-40C ₄N ₈) ^aThe atomic coordinate of the hydrogen atom in the crystal

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4x
	Negatively charged ion
????H 1a????H 2a????H 3a????H 4a????H 1b????H 2b????H 3b????H 4b????H 1c????H 2c????H 3c????H 4c????H 1d????H 2d					????1061 ????3182 ????4547 ????3162 ?????637 ????2692 ????4453 ????3373 ????-326 ???-2637 ???-4426 ???-3137 ????1070 ?????349	????3165 ????3406 ????2153 ????1162 ?????254 ?????174 ????1179 ????1775 ????2281 ????2453 ????2031 ????1655 ????2197 ????3499	????1756 ????1151 ????1428 ????2059 ????4479 ????6022 ????5753 ????4016 ?????132 ???-1199 ????-243 ????1623 ????4997 ????5480

Table 13 (continuing)

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4x
	?H 2ga?H 2gb?H 3ga?H 3gb?H 4ga?H 4gb?H 1ha?H 1hb?H 2ha?H 2hb?H 3ha?H 3hb?H 4ha?H 4hb?H 11a?H 11b?H 21a?H 21b?H 3ia?H 3ib?H 4ia	????6629 ????7629 ????6644 ????7102 ????4960 ????4493 ?????596 ?????921 ????2205 ????1449 ????3066 ????3908 ????4260 ????3874 ????3007 ????1721 ????3703 ????2496 ????1541 ????2638 ?????101	????2283 ????2940 ????2947 ????3717 ????4045 ????3223 ????4950 ????5310 ????6231 ????6034 ????5447 ????5936 ????4953 ????4459 ????1289 ????1306 ????2328 ????2303 ????3249 ????3195 ????2580				????5371 ????5209 ????6766 ????6322 ????5839 ????6118 ????2301 ????3451 ????3073 ????1874 ????1684 ????2669 ????3725 ????2671 ???-1594 ???-2615 ???-2031 ???-3103 ???-2509 ???-1381 ???-2020

Table 13 (continuing)

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4x
	?H 3d?H 4d?H 1e?H 2e?H 3e?H 4e?H 1fa?H 1fb?H 2fa?H 2fb?H 3fa?H 3fb?H 4fa?H 4fb	????-1115 ????-1278 ????-1346 ?????-630 ?????1503 ?????1999 ????-1447 ????-2359 ????-4069 ????-3468 ????-2341 ????-3620 ????-2417 ????-1165	????4135 ????3184 ?????578 ????-712 ???-1135 ????-107 ????1250 ????1762 ?????899 ?????674 ????-312 ????-314 ?????184 ????-201				????3762 ????2317 ?????293 ????-243 ????1285 ????2676 ????4520 ????3588 ????3170 ????3480 ????4022 ????2996 ????1980 ????2831
The crystallization solvent
				?H 1ga?H 1gb	????6103 ????5503	????3536 ????2694	????4135 ????3909

Table 13 (continuing)

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4x
	????H 4ib????H 1ja????H 1jb????H 2ja????H 2jb????H 3ja????H 3jb????H 4ja????H 4jb	????1010 ????4929 ????4341 ????5823 ????5232 ????3930 ????4261 ????2185 ????2215	????2761 ?????513 ?????-91 ????-388 ????-992 ???-1396 ????-668 ????-862 ????-324				????-851 ?????470 ????1129 ????-178 ?????479 ???-1018 ???-1623 ????-715 ???-1678

The a hydrogen atom (supposes that carbon is former as " taking " desirable atom on its corresponding carbon atom

Son produces SP ²-or SP ³Hydridization, and c h bond is 0.96 ) bag

Draw together in the calculating of textural factor.The isotropy thermal parameter of each hydrogen atom is fixing

, for its with the covalent linkage effective homogeneity thermal parameter of bonded carbon atom with it

1.2 doubly.The b hydrogen atom uses numeric suffix identical with its carbon atom and literal subscript to mark, but needs

Will the time also add in addition-literal subscript (a or b) with the difference with same carbon atom bonded

Each hydrogen atom.

Table 14 relates to (Cr (NC ₄N ₄) ₅(OC ₄N ₈)) (Na) ₂-4OC ₄N ₈ ^aThe bond distance of the non-hydrogen atom in the crystal

Kind b	Bond distance A	Kind b	Bond distance A
				????Cr-N 1a????Cr-N 1b????Cr-N 1c????Cr-N 1d????Cr-N 1e????Cr-O 1f????N 1a-C 1a????N 1a-C 4a????N 1b-C 1b????N 1b-C 4b????N 1c-C 1c????N 1c-C 4c????N 1d-C 1d????N 1d-C 4d????N 1e-C 1e????N 1e-C 4e	2.035(6) 2.056(5) 2.044(5) 2.114(6) 2.024(6) 2.120(5) 1.36(1) 1.38(1) 1.33(1) 1.37(1) 1.41(1) 1.35(1) 1.34(1) 1.36(1) 1.40(1) 1.39(1)	????N a1-C 1g????Na 1-O 1h????Na 2-O 1i????Na 2-O 1j????C 1g-C 2g????C 2g-C 3g????C 3g-C 4g????C 1h-C 2h????C 2h-C 3h????C 3h-C 4h????C 1i-C 2i????C 2i-C 3i????C 3i-C 4i????C 1j-C 2j????C 2j-C 3j????C 3j-C 4j	????2.314(6) ????2.271(8) ????2.365(7) ????2.307(7) ????1.33(2) ????1.43(2) ????1.47(2) ????1.51(2) ????1.30(2) ????1.48(2) ????1.4(3) ????1.47(3) ????1.40(3) ????1.44(2) ????1.46(2) ????1.42(2)

Table 14 (continuing)

Kind b	Bond distance A	Kind b	Bond distance A
				????O 1f-C 1f????O 1f-C 4f????C 1a-C 2c????C 2a-C 3a????C 3a-C 4a????C 1b-C 2b????C 2b-C 3b????C 3b-C 4b????C 1c-C 2c????C 2c-C 3c????C 3c-C 4c????C 1d-C 2d????C 2d-C 3d????C 3d-C 4d????C 1e-C 2e	????1.42(1) ????1.44(1) ????1.39(1) ????1.38(1) ????1.37(1) ????1.33(1) ????1.42(1) ????1.31(1) ????1.37(1) ????1.41(1) ????1.39(1) ????1.37(1) ????1.40(1) ????1.34(1) ????1.37(1)	????O 1g-C 1g????O 1g-C 4g????O 1h-C 1h????O 1i-C 1i????O 1i-C 4i????O 1j-C 1j????O 1j-C 4j????N2 1C 1a????Na 1-N 1d????Na 1-C 1d????Na 2-C 4a????Na 2-C 1e	????1.38(1) ????1.32(1) ????1.38(1) ????1.39(2) ????1.36(2) ????1.40(1) ????1.41(1) ????1.43(1) ????2.678(8) ????2.688(7) ????2.621(9) ????2.687(7) ????2.630(9)

Table 14 (continuing)

Kind b	Bond distance A	Kind b	Bond distance A
				????C 2e-C 3e????C 3e-C 4e????C 1f-C 2f????C 2f-C 3f????C 3f-C 4f	????1.43(1) ????1.37(1) ????1.50(1) ????1.43(2) ????1.49(2)

Numeral in a parenthesis is the rare estimation standard deviation of last significant figure.

The mark of b atom is consistent with Fig. 1.

The bond angle of the non-hydrogen atom in table 15 crystal (Cr (NC ₄N ₄) _s(OC ₄N ₈)) (Na) ₂-4OC ₄N ₈ ^a

Kind b	The bond angle degree	Kind b	The bond angle degree
				????N 1aCrN 1b????N 1aCrN 1c????N 1aCrN 1d????N 1aCrN 1e????N 1aCrO 1f????N 1bCrN 1c????N 1bCrN 1d????N 1bCrN 1e????N 1bCrO 1f????N 1cCrN 1d????N 1cCrN 1e????N 1cCrO 1f????N 1dCrN 1e????N 1dCrO 1f????N 1eCrO 1f????CrN 1aC 1a	????91.2(2) ????91.4(2) ????91.1(2) ????92.8(2) ????178.7(2) ????176.2(2) ????86.7(2) ????93.3(2) ????88.5(2) ????90.4(2) ????89.4(2) ????88.8(2) ????176.1(2) ????87.6(2) ????88.5(2) ????128.7(5)	????O 1gNa 1O 1h????O 1gNa 1C 1a????O 1gNa 1C 1a????O 1gNa 1C 1d????O 1hNa 1C 1a????O 1hNa 1N 1d????O 1hNa 1C 1d????C 1aNa 1N 1d????C 1aNa 1C 1d????N 1dNa 1C 1d????O 1iNa 2O 1j????O 1iNa 2C 4a????O 1iNa 2C 1e????O 1jNa 2C 4a????O 1jNa 2C 1e????C 4aNa 2C 1e	?????92.3(3) ????114.3(3) ????139.6(3) ????118.0(3) ?????95.6(3) ????127.0(2) ????132.1(3) ?????75.1(2) ????103.1(3) ?????29.3(2) ?????90.7(3) ????109.3(3) ????131.5(2) ????103.3(2) ????115.1(3) ????103.9(3)

Table 15 (continuing)

Kind b	The bond angle degree	Kind b	The bond angle degree
				????CrN 1aC 4a????CrN 1bC 1b????CrN 1bC 4b????CrN 1cC 1c????CrN 1cC 4c????CrN 1dC 1d????CrN 1dC 4d????CrN 1eC 1e????CrN 1e4 e????CrO 1fC 1f????CrO 1fC 4f????C 1aN 1aC 4a????C 1bN 1bC 4b????C 1cN 1cC 4c????C 1dN 1dC 4d????C 1eN 1eC 4e????C 1fO 1fC 4f	????126.3(5) ????127.0(4) ????127.3(5) ????128.5(5) ????126.7(5) ????127.7(5) ????125.7(5) ????127.7(5) ????126.2(4) ????126.4(4) ????123.1(5) ????105.0(6) ????105.2(5) ????104.0(5) ????106.6(6) ????106.0(6) ????110.5(6)	?Na 1O 1gC 1g?Na 1O 1gC 4g?Na 1O 1hC 1h?Na 1O 1hC 4h?Na 2O 1iC 1i?Na 2O 1iC 4i?Na 2O 1jC 1j?Na 2O 1jC 4j?C 1gO 1gC 4g?C 1hO 1hC 4h?C 1iO 1iC 4i?C 1jO 1jC 4j?O 1gC 1gC 2g?C 1gN 2gC 3g?C 2gC 3gC 4g?C 3gC 4gO 1g?O 1hC 1hC 2h?C 1hC 2hC 3h	131.4(6) 124.0(8) 132.2(7) 116.6(6) 120.9(8) 126.8(7) 123.1(6) 128.8(5) 104.3(8) 108.9(9) 107.8(11) 107.7(7) 111(1) 103(1) 103(1) 110(1) 106(1) 106(1)

Table 15 (continuing)

Kind b	The bond angle degree	Kind b	The bond angle degree
				?N 1aC 1aC 2a?C 1aC 2aC 3a?C 2aC 3aC 4a?C 3aC 4aN 1a?N 1bC 1bC 2b?C 1bC 2bC 3b?C 2bC 3bC 4b?C 3bC 4bN 1b?N 1cC 1cC 2c?C 1cC 2cC 3c?C 2cC 3cC 4c?C 3cC 4cN 1c?N 1dC 1d2 2d?C 1dC 2dC 3d?C 2dC 3dC 4d?C 3dC 4dN 1d?N 1eC 1eC 2e?C 1eC 2eC 3e?C 2eC 3eC 4e	111.1(7) 106.1(8) 107.5(7) 110.3(7) 110.6(7) 107.6(8) 104.4(7) 112.2(7) 112.4(7) 104.5(7) 107.8(7) 111.2(7) 109.0(7) 107.6(8) 105.4(8) 111.5(7) 111.0(7) 105.2(7) 108.4(8)	?C 2hC 3hC 4h?C 3hC 4hO 1h?O 1iC 1iC 2i?C 1iC 2iC 3i?C 2iC 3iC 4i?C 3iC 3iO 1i?O 1jC 1jC 2j?C 1jC 2jC 3j?C 2jC 3jC 4j?C 3jC 4jO 1j?Na 1C 1aN 1a?Na 1C 1aC 2a?Na 1N 1dCr ?Na 1N 1dC 1d?Na 1N 1dC 4d?Na 1C 1dN 1d?Na 1C 1dC 2d	????109(1) ????106(1) ????110(2) ????105(2) ????106(2) ????107(1) ????106(1) ????109(1) ????104(1) ????108(1) ????95.0(4) ????106.7(5) ????107.7(3) ????72.6(4) ????86.4(4) ????78.1(4) ????85.1(6)

Table 15 (continuing)

Kind b	The bond angle degree	Kind b	The bond angle degree
				?C 3eC 4eN 1e?O 1fC 1fC 2f?C 1fC 2fC 3f?C 2fC 3fC 4f?C 3fC 4fO 1f	?109.5(7) 104.4(7) 105.0(9) 104.9(9) 104.7(7)	?Na 2C 4aN 1a?Na 2C 4aC 3a?Na 2C 1eN 1e?Na 2C 1eC 2e	????96.2(3) ???104.0(5) ????78.1(4) ????91.7(6)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1.

Embodiment 7

Be used to prepare active catalyst, by 2,5-dimethyl pyrrole sodium and Crcl ₂The product that reacts and get is a kind of light blue solid-product VI.With 2,5-dimethyl pyrrole (5.0 milliliters/49.1 mmole) mixes in tetrahydrofuran (THF) (125 milliliters) at ambient temperature with excessive sodium (40% dispersion liquid in petroleum solvent) refluxed 12 hours this mixture under nitrogen atmosphere, filter then to remove superfluous sodium.2 of gained, 5-dimethyl pyrrole sodium in-field use mixes at ambient temperature with chromous chloride (3.03 grams/24.7 mmoles).The reaction mixture of gained was refluxed 48 hours under nitrogen atmosphere.The greyish-green solution of gained is filtered at ambient temperature (with the frit of medium porosity), and vacuumize to remove and desolvate, vacuum-drying is 12 hours then, generates ash/green solid.Wash this ash/green solid with pentane then, obtain light blue solid-product VI, collect this product by filtering.The product VI does not need further purification just to be used to prepare active catalyst.

Embodiment 8

Preparation of catalysts

All aggregation tests all carry out in one 2 liters of reactors under slurry (particulate form) condition.Thinner is a Trimethylmethane, and temperature of reactor is 90 ℃, as required ethene is fed in polymerization process, makes the pressure of reactor remain 550 pounds/inch ²(3793kPa)

The actual charging of reactor is finished with following method.Down after at least 15 minutes, the temperature of reactor is reduced to 90 ℃ at 100 ℃, and the Chromium pyrrolate catalyzer of the band carrier that will weigh in advance in the countercurrent direction of small amount of nitrogen air-flow adds with nitrogen gas stream cleaning reaction devices.Then 1 liter of Trimethylmethane is added reactor, and logical at last ethene makes the reactor pressurising.

The consumption of ethene is with a precalibrated ethylene stream flowmeter measurement.After test is carried out 30 minutes, under the situation that does not make the reactor decompression, take out product liquid mixture sample.Its way is to make the sampling steel cylinder pressurising that is connected to reactor to 200-300 pound/inch with a dip-tube that porous tip is housed and reaches reactor bottom ²(1379-2069kPa) (gauge pressure).The sample of Qu Chuing is analyzed with vapor-phase chromatography and gas chromatography-mass spectrography like this.Selectivity is normalized to 100%.Make the reactor exhaust, communicate, and liquid is separated with solid matter, so just obtain solid product with decanting process with atmosphere.Then this solid is placed vacuum drying oven down dry and weigh at 100 ℃. weigh up solid and relict catalyst mixture gross weight and deduct the catalyzer add-on of weighing in advance, just try to achieve the output of solid product. the ethene consumption of writing down under meter restrains the output that number deducts solid product, just obtains the output of volatile products.

General according to 30 minutes test period activity calculated, shown in table X VI, for 300-1500 gram product/gram catalyzer/hour.General 97-99.5% (weight) is a liquid in the product that obtains, and 0.5-3% (weight) is polymkeric substance (wax).Generally, 85% in the liquid distillate gross weight is that hexene, 11% is that decene, 2% is tetradecene.The rest part of product liquid mixture is that the trace level of alkene distributes, and its total amount accounts for the 1-2% (weight) of product mixtures, sees Table the X VII.

Deactivated catalyst is prepared as follows by the Chromium pyrrolate complex compound.Used whole toluene and (or) the pentane rinsing liquid is about the 15-30 milliliters of liquid.

Test 1:

Under nitrogen wash,, be heated to 80 ℃, and kept 4 hours,, make slurry with 15 milliliters of toluene at ambient temperature then to remove remaining THF with 0.158 gram product V (in the THF solvent, preparing).With 9.0 milliliters be dissolved in hexane by 1MTEA and solution add in the slurry of gained and stirred 24 hours.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 2.00 gram AlPO ₄(the P/Al mol ratio is 0.4) and restir 24 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with toluene with its rinsing twice, and then with twice of pentane rinsing.0.3143 this catalyzer of gram is directly added in the reactor to carry out polymerization.After adding catalyzer, but adding Trimethylmethane (reactor solvent) before, 1.0 milliliters 0.5%TEA n-heptane solutions are being added in the reactor to remove material toxicity.

Test 2:

Under nitrogen wash, 0.081 gram product V (preparing in the THF solvent) is heated to 80 ℃, and kept 4 hours, to remove remaining THF, make slurry with 15 milliliters of diethylbenzene at ambient temperature then.With 20 milliliters be dissolved in hexane by 1MTEA and solution add in the slurry of gained, and stirred 24 hours.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 1.50 gram AlPO ₄(the P/Al mol ratio is 0.4) and restir 1 hour.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with dimethylbenzene with its rinsing twice, and then with twice of pentane rinsing.0.4333 this catalyzer of gram is directly added in the reactor to carry out polymerization.After adding catalyzer, just adding Trimethylmethane (reactor solvent) before, 3.0 milliliters 0.5%TEA n-heptane solutions are being added in the reactor to remove material toxicity.

Test 3:

With 15 milliliters of toluene 0.093 gram product V (preparing) is made slurry at ambient temperature in the DME solvent.Add 5.0 milliliters 1MTEA hexane solutions in this slurry and stirred 24 hours.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 1.0 gram AlPO ₄(the P/Al mol ratio is 0.4) and restir 24 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.0.1564 this catalyzer of gram is directly added in the reactor to carry out polymerization.After adding catalyzer, but adding Trimethylmethane (reactor solvent) before, 3.0 milliliters 0.5%TEA n-heptane solutions are being added in the reactor to remove material toxicity.

Test 4:

With 15 milliliters of toluene 0.080 gram product I (preparing) is made slurry at ambient temperature in the THF solvent.Add 6.0 milliliters 1MTEA hexane solution, and stirred 16 hours.Generate brown solution immediately after adding TEA, the product I is dissolved fully.In this solution, add 1.50 gram AlPO ₄(the P/Al mol ratio is 0.4), and restir 16 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.1.1988 these catalyzer of gram are directly added in the reactor to carry out polymerization.

Test 5:

With 15 milliliters of toluene 0.079 gram product II (preparing) is made slurry at ambient temperature in the THF solvent.Add 2.0 milliliters 1.9M TEA toluene solutions in this slurry and stirred 8 hours.Generate brown solution immediately after adding TEA, the product II is dissolved fully.In this solution, add 0.50 gram AlPO ₄(the P/Al mol ratio is 0.4), and restir 16 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.0.4829 this catalyzer of gram is directly added in the reactor to carry out polymerization.

Test 6:

At ambient temperature, with 15 milliliters of toluene 0.071 gram is heated to 80 ℃ under nitrogen wash, and kept 4 hours, make slurry with the product V (tie up in the THF solvent and make) of removing remaining THF.2.0 milliliters are added in this slurry by the 1MTEA hexane solution and stirred 1 hour.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 2.52 gram SiO ₂And restir 2 minutes.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.Whole catalyzer are directly added in the reactor to carry out polymerization.

Test 7:

With 15 milliliters of toluene 0.103 gram product II (preparing) is made slurry at ambient temperature in the THF solvent.In this slurry, add 1.0 milliliters 1.9M TEA toluene solution and stirred 10 minutes.Generate brown solution immediately after adding TEA, the product II is dissolved fully.In this solution, add 2.27 gram AlO, and restir 2 minutes.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.1.2926 these catalyzer of gram are directly added in the reactor to carry out polymerization.

Test 8:

With 15 milliliters of toluene 0.120 gram product I (preparing) is made slurry at ambient temperature in the THF solvent.In this slurry, add 2.0 milliliters 1MTEA toluene solution and stirred 2 days.Generate brown solution immediately after adding TEA, the product I is dissolved fully.In this solution, add 1.0 gram SiO ₂And 3 weeks of restir.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.Whole catalyzer are directly added in the reactor to carry out polymerization.

Test 9:

With 15 milliliters of toluene the product III of 0.106 gram (preparing) is made slurry at ambient temperature in the THF solvent.In this slurry, add 2.5 milliliters 1.9MTEA toluene solution and stirred 2 hours.Generate brown solution immediately after adding TEA, the product III is dissolved fully.In this solution, add 0.65 gram AlPO ₄(the P/Al mol ratio is 0.4), and restir 2 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.All catalyzer are directly added in the reactor to carry out polymerization.After adding catalyzer, but adding Trimethylmethane (reactor solvent) before, 1.5 milliliters of 1.0%TEA pentane solutions are being added in the reactor to remove material toxicity.

Test 10:

At ambient temperature, 0.030 gram is heated to 80 ℃ under nitrogen wash, and keeps making slurry with the product V (tie up in the THF solvent and make) of removing remaining THF in 4 hours with 15 milliliters of toluene.In this slurry, add 3.0 milliliters of 1MTEA hexane solutions and stirred 16 hours.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 2.0 gram AlPO ₄(the P/Al mol ratio is 0.9) and restir 16 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.0.322 this catalyzer of gram is directly added in the reactor to carry out polymerization.

Test 11:

With 15 milliliters of pentanes the product V that 0.067 gram makes is made slurry at ambient temperature in the THF solvent.In this slurry, add 4.0 milliliters 1MTEA hexane solution and stirred 24 hours.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 1.0 gram AlPO ₄(the P/Al mol ratio is 0.4), and restir 24 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid,, with its rinsing twice all catalyzer is directly added in the reactor to carry out polymerization with pentane.After adding catalyzer, but adding Trimethylmethane (reactor solvent) before, 3.0 milliliters of 0.5%TEA n-heptane solutions are being added in the reactor to remove material toxicity.

Test 12:

At ambient temperature, 0.073 gram is heated to 80 ℃ under nitrogen wash, and keeps making slurry with the product V (tie up in the THF solvent and make) of removing remaining THF in 4 hours with 15 milliliters of toluene.In this slurry, add 6.0 milliliters of 1MTEA hexane solutions and stirred 24 hours.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 7.0 gram P/SiO ₂, and restir 24 hours, solution is almost decoloured.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.2.85 these catalyzer of gram are directly added in the reactor to carry out polymerization.

Test 13:

With 15 milliliters of diethylbenzene 0.125 gram product II is made slurry at ambient temperature.Add 9.0 milliliters of 1MTEA hexane solutions in this slurry and stirred 8 hours.Generate brown solution immediately after adding TEA, the product II is dissolved fully.With 2.0 gram F/Al ₂O ₃Add in this solution and restir 12 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.0.5477 this catalyzer of gram is directly added in the reactor to carry out polymerization.

Test 14:

With 15 milliliters of toluene 0.125 gram product IV is made slurry at ambient temperature.Add 1.5 milliliters of 1MTEA hexane solutions in this slurry and stirred 10 minutes.Generate red/brown solution immediately after adding TEA, the product IV is dissolved fully.In this solution, add 2.0 gram SiO ₂And restir 1 minute, almost make the solution decolouring.From solution, leach the band carrier SiO 2 catalyst, it be a kind of red/brown solid, with its rinsing twice, then use twice of pentane rinsing with toluene again.All catalyzer are directly added in the reactor to carry out polymerization.

Test 15:

With 15 milliliters of glycol dimethyl ether dissolvings, 0.30 gram product V (tie up in the DME solvent and prepare), generate green solution.Make this solution and AlPO ₄(the P/Al mol ratio is 0.4) (2.00 gram) mixes, and mixture was stirred 1 hour.From solution, leach the material of green band carrier, with glycol dimethyl ether rinsing and dry down at 90 ℃ under nitrogen cleans.This material and 15 milliliters of toluene and 3 milliliters of triethyl aluminums (Aldrich 1.0M, hexane) are mixed, and restir 3 hours.Filter and collect brown band carried catalyst, use the pentane rinsing, carry out vacuum-drying then.0.4609 this catalyzer of gram is directly added in the reactor to carry out polymerization.After adding catalyzer, but adding Trimethylmethane (reactor solvent) before, 3.0 milliliters of 0.5%TEA n-heptane solutions are being added in the reactor to remove material toxicity.

Test 16:

At ambient temperature, 0.058 gram is heated to 80 ℃ under nitrogen wash, and keeps making slurry with the product V (tie up in the THF solvent and make) of removing remaining THF in 4 hours with 15 milliliters of benzene.Add 4.0 milliliters of 1MTEA hexane solutions in this slurry and stirred 2 hours.Generate brown solution immediately after adding TEA, the product V is dissolved fully.In this solution, add 1.0 gram AlPO ₄(the P/Al mol ratio is 0.4) also stirred 1 hour.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with benzene again.All catalyzer are directly added in the reactor to carry out polymerization.After adding catalyzer, but adding Trimethylmethane (reactor solvent) before, 3.0 milliliters of 0.5%TEA n-heptane solutions are being added in the reactor to remove material toxicity.

Test 17:

Under 90 ℃, 0.1610 gram product I is directly added in the reactor.1 liter of Trimethylmethane is housed in the reactor, and is pressurized to 550 pounds/inch with ethene ²(3793kPa) (gauge pressure). do not measure ethene and consumed, therefore in reactor, fed 50 pounds/inch ²(345kPa) (gauge pressure) hydrogen, but consumption of ethylene not yet just just begin consumption of ethylene after 2.0 milliliters of 1M TEA hexane solution are added.

Test 18:

Under 90 ℃, 0.3528 gram product VI is directly added in the reactor.1 liter of Trimethylmethane is housed in the reactor, and is pressurized to 550 pounds/inch with ethene ²(345kPa) (gauge pressure).Do not measured ethene and consumed, therefore 2.0 milliliters of 1M TEA hexane solutions have been added, this makes ethene begin to consume.

Test 19:

Under 90 ℃, 0.3428 gram product VI is directly added in the reactor.Before adding 1 liter of Trimethylmethane, 2.0 milliliters of 1M TEA hexane solutions are housed also in the reactor.Feeding ethene then makes reactor be pressurized to 550 pounds/inch ²(3793kPa) (gauge pressure).Do not measured ethene and consumed, therefore with 30 pounds/inch ²Hydrogen (207kPa) feeds in the reactor, makes ethene begin to consume.

Test 20:

At ambient temperature with 0.202 gram product V (in glycol dimethyl ether (DME) solvent, making), 6.0 milliliters of 1.9M TEA toluene solutions and 2.0 gram AlPO ₄(the P/Al mol ratio is 0.4) mixes with 15 milliliters of toluene.Generate brown solution after the mixing immediately, the product V is dissolved fully.This brown solution was stirred 48 hours.Leach the catalyzer of band carrier from solution, it is a kind of brown solid, with its rinsing twice, then uses twice of pentane rinsing with toluene again.0.0671 gram catalyzer is directly added in the reactor to carry out polymerization.After adding catalyzer, but adding Trimethylmethane (reactor solvent) before, 1.0 milliliters of 0.5%TEA n-heptane solutions are being added in the reactor to remove material toxicity.

Data in the table X VI show that chromium cpd of the present invention maybe can be with carrier (test 1-16,20) or can not be with carrier (test 17-19), be used for alkene polymerization and (or) trimerization.In addition, can change condition for the output that increases the trimer product (test 1-5 and 9) or the output (test 6,7 and 13) that improves solid product or polymkeric substance.Test 1,3 and 20 shows can obtain very high activity.

Table 16

Test a	Catalyzer	Carrier b	Product	Active c
					????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13	(V)/TEA/ toluene (V) TEA/ diethylbenzene "/toluene "/toluene " " " " " " "/pentane "/toluene "/diethylbenzene	AIPO 4?″ ????″ ????″ ????″ SiO 2Al 2O 3SiO 2AIPO 4AIPO 4(.9) AIPO 4P/SiO 2F/AI 2O 3	98.4% liquid, 1.6% solid, 99.4% liquid, 0.6% solid, 99.4% liquid, 0.6% solid, 98.6% liquid, 1.4% solid, 98.2% liquid, 1.8% solid, 89.0% liquid, 11.0% solid, 55.8% liquid, 44.2% solid, 93.3% liquid, 6.7% solid, 99.8% liquid, 0.2% solid, 96.8% liquid, 3.2% solid (trace) liquid, (trace) solid 98.1% liquid, 1.9% solid, 88.0% liquid, 12.0% solid	???1030 ????730 ??1450d ????360 ????580 ?????80 ?????50 ????400 ????100 ????930 ?????90 ????300

Table 16 (continuing)

Test a	Catalyzer	Carrier b	Product	Active c
					????14 ????15 ????16 ????17 ????18 ????19 ????20	(VI) TEA/ toluene, (V)/DME, (V)/TEA/ benzene, (I)/TEA, (VI)/TEA, (VI)/TEA, (V)/TEA	SiO 2AIPO 4The AIPO that " is not with carrier " 4	94.3% liquid, 5.7% solid, 98.0% liquid, 2.0% solid, 99.1% liquid, 0.9% solid, 98.3% liquid, 1.7% solid, 99.4% liquid, 0.6% solid, 98.1% liquid, 1.9% solid, 99.5% liquid, 0.5% solid	????40 ????550 ????500 ????340 ????180 ????230 ????2760

All tests of a A II are all at 90 ℃, 550 pounds/inch ²Total pressure under in the Trimethylmethane solvent, carry out.B P/Al mol ratio=0.4, but test 10 its P/Al mol ratio=0.9 of exception.Activity when the c test period is 30 minutes, unit for the gram product/gram chromium/hour.D is owing to testing error, and this value is lower than actual value, estimates that its actual value is near 2000.

Table 17

Test	????C4	The 1-hexane	????C6	????C8	????C10	????C12	????C14	????C16-C28
									????1 ????2 ????3 ????5 ????6 ????16 ????19	????0.05 ????0.10 ????0.06 ????0.1 ????0.55 ????0.06 ????6.03	????81.92 ????78.80 ????82.19 ????83.40 ????78.70 ????72.85 ????71.66	????7.76 ????7.49 ????7.68 ????7.08 ????5.52 ????13.61 ????6.09	????0.49 ????0.58 ????0.45 ????0.62 ????1.84 ????0.11 ????3.61	????9.12 ???11.36 ????8.85 ????8.08 ????11.24 ????12.06 ????9.42	????0.09 ????0.10 ????0.08 ????0.05 ????0.42 ????0.09 ????1.17	????0.52 ????0.01 ????0.58 ????0.42 ????1.26 ????0.93 ????1.41	????0.05 ????0.56 ????0.11 ????0.25 ????0.47 ????0.09 ????0.61

The embodiment IX

Fig. 7 and 8 is depicted as Cr (NC ₄H ₄) ₃Cl (O ₂C ₂H ₄(CH ₃) ₂) ₃The monocrystalline x-ray structure of Na Figure 9 shows that Cr (NC ₄H ₄) ₃Cl (O ₂C ₂H ₄(CH ₃) ₂) the monocrystalline x-ray structure.These crystal all are to obtain according to the method shown in the embodiment III.But the crystal with X ray feature is then obtaining under envrionment temperature and the pressure and after keeping about 2 days under the nitrogen inert atmosphere deep green filtrate.

To C ₂₄H ₄₂N ₃O ₆The result that CrNaCl analyzes is:

Calculation result: C49-78; H7.31; N7.26% (weight)

Measured result: C49.80; H7.39; N7.18% (weight)

About collecting being described below of used monocrystalline sample of data and crystal cup:

Color: green-Hei

Shape: rectangular parallelepiped

Size: 0.44 * 0.62 * 0.62 millimeter

Crystal cup: crystal is bonded in the thin-walled glass hair coin inside pipe wall that fills nitrogen

Crystalline orientation: make one of crystalline longer sides almost parallel with the phi axle of diffractometer.

The width at half place of ω scanning height: 0.38 °

The data of spacer and structure cell are as follows:

Crystallographic system: oblique crystal

Spacer and space-number ²: P2 _l/ C-C ⁵ _2h(No.14)

The computer center's reflection number that is used for the least-squares refinement of unit cell dimension:

15?20＞25°℃=20+1

Lattice parameter and effective standard deviation thereof

a=8.135(2)???????α=90.00°???????v=3027(1) ³

b?=?22.337(5)????β=91.67(2)°????z=4

c=16.667(4)??????γ=?90.00°??????λ?=?0.71073

Molecular weight: 579.05amu

Molecular weight: 579.05 atomic mass units

Bulk density: 1.271 gram per centimeters ³

Linear absorption coefficient: 0.51 millimeter ^-1

Table X VIII-XII has been listed in order to produce the gained parameter of the molecular structure shown in Fig. 7 and 8.

Table 18 (Cr (NC ₄H ₄) ₃(Cl) (O ₂C ₂H ₄(CH ₃) ₂) ₃Na) ^aThe atomic coordinate of the non-hydrogen atom in the crystal

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					??10 4x	??????10 4y	??10 4z
	??Cr ??Cl ??Na ??Nl ?C 11?C 12?C 13?C 14??N 2?C 21?C 22?C 23?C 24??N 3?C 31?C 32	-1030(1) ??135(1) -2167(2) -3062(4) -4107(5) -5189(5) -4810(5) -3512(5) -1817(4) -1188(6) -2205(7) -3499(7) -3248(5) -1892(4) -3100(5) -3573(6)	?????559(1) ?????-26(1) ???-1011(1) ??????65(2) ??????63(2) ????-409(2) ????-713(2) ????-414(2) ????1027(2) ????1558(2) ????1790(2) ????1398(2) ?????934(2) ????1185(2) ????1588(2) ????1901(2)					3005(1) 1981(1) 1832(1) 2907(2) 2251(3) 2291(3) 2998(3) 3361(3) 3950(2) 4234(2) 4799(3) 4874(3) 4349(2) 2260(2) 2434(3) 1757(3)	????30(1) ????41(1) ????46(1) ????35(1) ????40(1) ????51(1) ????51(1) ????46(1) ????37(1) ????47(1) ????60(2) ????60(2) ????43(1) ????35(1) ????41(1) ????53(1)

Table 18 (continuing)

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					??10 4x	??10 4y	?10 4z
	?C 33?C 34?O 1a?O 2a?C 1a?C 2a?C 3a?C 4a?O 1b?O 2b?C 1b?C 2b?C 3b?C 4b	-2631(6) -1620(6) ?1317(3) ??153(3) ?2459(5) ?1443(6) ?2156(6) ??653(6) -2558(4) -3877(5) -3618(9) -3627(9) -2410(8) -4149(9)	1686(2) 1249(2) 971(1) -12(1) 631(2) 329(2) 1247(2) -625(2) -783(2) -1772(2) -1166(3) -1765(3) -207(3) -2328(3)					1130(3) 1453(3) 3154(2) 3878(2) 3651(3) 4268(3) 2495(3) 3733(3) ?398(2) 1111(2) ?-25(4) ?302(4) ??61(4) 1440(5)	????51(1) ????46(1) ????40(1) ????40(1) ????53(1) ????53(1) ????58(2) ????49(1) ????62(1) ????76(1) ????89(2) ????83(2) ????79(2) ???106(3)

Table 18 (continuing)

Atomic species b	Fractional coordinates			The effective homogeneity thermal parameter
					???????10 4x	????10 4y	???10 4z
	?O 1c?O 2c?C 1c?C 2c?C 3c?C 4c	???-1334(4) ?????235(5) ??????71(7) ?????951(8) ???-2090(8) ????1224(8)	-1823(2) -1589(2) -2144(3) -1913(4) -2017(3) -1393(3)					2911(2) 1529(3) 2724(4) 2067(4) 3614(4) ?900(4)	????65(1) ????87(2) ????83(2) ????107(3) ????83(2) ????88(2)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1.

C is 1/3 of a Bij tensor.

Table 19 (Cr (NC ₄H ₄) ₃(Cl) (O ₂C ₂H ₄(CH ₃) ₂Na) ^{A ' b}The anisotropy thermal parameter of the non-hydrogen atom in the crystal

Atomic species c	Anisotropy thermal parameter (A 2×10)
							????B 11	????B 22	????B 33	????B 12	????B 13	????B 23
	????Cr ????Cl ????Na ????N 1????C 11????C 12????C 13????C 14????N 2????C 21????C 22????C 23????C 24	????28(1) ????39(1) ????47(1) ????31(1) ????31(2) ????33(2) ????35(2) ????39(2) ????36(2) ????55(2) ????88(3) ????65(3) ????37(2)	????31(1) ????43(1) ????48(1) ????39(2) ????47(2) ????59(3) ????39(2) ????45(2) ????38(2) ????38(2) ????46(3) ????74(3) ????55(2)	????30(1) ????41(1) ????44(1) ????35(2) ????41(2) ????61(3) ????79(3) ????54(2) ????36(2) ????47(2) ????44(2) ????42(2) ????37(2)	????2(1) ????2(1) ????0(1) ????0(1) ????0(2) ???-3(2) ???-6(2) ????1(2) ????7(1) ????9(2) ????32(2) ????32(2) ????14(2)	????-0(1) ?????5(1) ?????3(1) ?????2(1) ????-1(2) ????-4(2) ?????8(2) ?????2(2) ????-3(1) ????-6(2) ????-9(2) ?????7(2) ????-0(2)							????-2(1) ????19(1) ????-4(1) ????-3(1) ????-7(2) ???-16(2) ?????3(2) ????10(2) ????-8(1) ????-5(2) ???-12(2) ?????0(2) ?????1(2)

Table 19 (continuing)

Atomic species c	Anisotropy thermal parameter (A 2×10)
							B 11	?B 22	????B 33	????B 12	????B 13	????B 23
	????N 3????C 31????C 32????C 33????C 34????O 1a????O 2a????C 1a????C 2a????C 3a????C 4a????C 1b????C 2b????C 1b????C 2b	38(2) 35(2) 52(2) 62(3) 52(2) 32(1) 40(1) 33(2) 53(2) 45(2) 50(2) 76(2) 101(3) 120(5) 116(5)	????35(2) ????43(2) ????47(2) ????51(3) ????45(2) ????40(1) ????38(1) ????50(3) ????55(3) ????53(3) ????40(2) ????63(2) ????62(2) ????91(4) ????64(3)	????32(2) ????43(2) ????58(3) ????39(2) ????40(2) ????50(2) ????41(1) ????73(3) ????51(2) ????76(3) ????58(3) ????47(2) ????63(2) ????56(3) ????68(4)	?????3(1) ?????6(2) ?????8(2) ????-2(2) ????-1(2) ????-1(1) ?????6(1) ?????4(2) ????10(2) ???-15(2) ????12(2) ???-14(2) ???-28(2) ???-29(4) ???-18(3)	?????0(1) ????-3(2) ???-11(2) ????-8(2) ?????2(2) ????-3(1) ????-7(1) ???-13(2) ???-24(2) ?????8(2) ????-8(2) ????-5(2) ????-5(2) ???-25(3) ???-24(3)							????-0(1) ?????1(2) ?????6(2) ????12(2) ?????2(2) ????-5(1) ????-1(1) ???-10(2) ???-10(2) ????-5(3) ????-1(2) ?????1(2) ????-2(2) ????-3(3) ???-12(3)

Table 19 (continuing)

Atomic species c	Anisotropy thermal parameter (A 2×10)
							??????B 11	??B 22	??B 33	????B 12	????B 13	????B 23
	????C 3b????C 4b????O 1c????O 2c????C 1c????C 2c????C 3c????C 4c	????81(4) ???118(5) ????61(2) ????74(2) ????73(3) ????83(4) ????84(4) ????77(4)	????84(4) ????84(4) ????64(2) ????76(3) ????65(3) ???143(6) ????64(3) ????98(5)	?72(4) 113(5) ?70(2) 112(3) 113(5) 96(5) 101(5) ?90(5)	?????-9(3) ????-51(4) ?????8(2) ????29(3) ????23(3) ????61(4) ????-8(3) ????13(3)	????-1(3) ???-38(4) ?????0(2) ????31(2) ?????9(3) ????24(4) ?????3(4) ????29(3)							????19(3) ????29(4) ?????4(2) ????30(2) ????25(3) ????14(5) ????16(3) ????-5(4)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The form of b anisotropy thermal parameter sees that crystal structure analysis reports the note 8 on the 6th page.

The mark of c atom is consistent with Fig. 1.

Table 20 (cr (NC ₄H ₄) ₃(Cl) (O ₂C ₂H ₄(CH ₃) ₂) ₃Na) ^aThe atomic coordinate of the hydrogen atom in the crystal

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4z
	????H 11????H 12????H 13????H 14????H 21????H 22????H 23????H 24????H 31????H 32????H 33????H 34????H 1aa????H 1ab????H 2aa	????-4089 ???-60043 ????-5349 ????-2993 ?????-188 ????-2044 ????-4404 ????-3967 ????-3554 ????-4392 ????-2680 ?????-840 ?????3014 ?????3254 ??????967 ?????2127	?????350 ????-509 ???-1064 ????-526 ????1740 ????2158 ????1441 ????-597 ????1644 ????2210 ????1817 ????1021 ?????339 ?????892 ?????626 ??????67				????1823 ????1905 ????3195 ????3863 ????4063 ????5089 ????5226 ????4273 ????2954 ????1720 ????581 ????1159 ????3336 ????3906 ????4606 ????4588

Table 20 (continuing)

Atomic species b	Fractional coordinates
				????10 4x	????10 4y	????10 4z
	????H 2ab????H 3aa????H 3ab????H 3ac????H 4aa????H 4ab????H 4ac????H 1ba????H 1bb????H 2ba????H 2bb????H 3ba????H 3bb????H 3bc????H 4ba????H 4bb????H 4bc????H 1ca????H 1cb	?????2127 ?????1391 ?????2589 ?????3040 ?????-256 ??????926 ?????1586 ????-4712 ????-3277 ????-2588 ????-4492 ????-1696 ????-3461 ????-1935 ????-4380 ????-3108 ????-4998 ??????795 ?????-255	???????67 ?????1487 ??????938 ?????1495 ?????-834 ?????-806 ?????-646 ????-1006 ????-1186 ????-1951 ????-1988 ???????26 ??????-14 ?????-243 ????-2289 ????-2524 ????-2561 ?????2146 ????-2547				????4588 ????2185 ????2162 ????2696 ????3484 ????4242 ????3395 ?????-11 ????-570 ?????204 ??????37 ?????407 ???????7 ????-458 ????2000 ????1385 ????1178 ????3189 ????2596

Table 20 (continuing)

Atomic species b	Fractional coordinates
				??????10 4x	?????10 4y	????10 4z
	????H 2ca????H 2cb????H 3ca????H 3cb????H 3cc????H 4ca????H 4cb????H 4cc	??????1398 ??????1831 ?????-3168 ?????-1397 ?????-2164 ???????456 ??????2033 ??????1756	????-2252 ????-1676 ????-1848 ????-1884 ????-2446 ????-1357 ????-1690 ????-1015				????1795 ????2294 ????3661 ????4055 ????3624 ?????454 ?????780 ?????996

All 6 first assistant officers of a are refined into has SP ³-hydridization geometrical shape and 0.96 C-H bond distance's rigid rofor.The original alignment of each methyl is according to the position finding of the different Fourier of hydrogen atom, the final orientation of each methyl is measured according to three rotation parameters, and the O-C-H bond angle of the exact position of rigid rotw methyl is that 103 °-115 ° all the other hydrogen atoms (suppose that carbon atom produces SP as " taking " desirable atom on its corresponding carbon atom ³-hydridization, and c h bond is long is 0.96A) be included in the calculating of textural factor. the isotropy thermal parameter of each hydrogen atom is a fixed, for its with covalent linkage 1.2 times of effective homogeneity thermal parameter of bonded carbon atom with it.The b hydrogen atom uses the subscript identical with its carbon atom to mark, but also adds a literal subscript (a, b or c) when needing in addition with difference and same each hydrogen atom of carbon atom bonded.Table 21 (Cr (NC ₄H ₄) ₃+ Cl) (O ₂C ₂H ₄(CH ₃) ₂) ₃Na) ^aThe bond distance of the non-hydrogen atom the in-crystal

Kind b	Bond distance	Kind b	Bond distance
				????Cr-Cl ????Cr-O 1a????Cr-O 2a????N 1-C 11????N 1-C 14????N 2-C 21????N 2-C 24????N 3-C 31????N 1-C 34????O 1a-C 1a????O 1a-C 1a????O 2a-C 2a????O 2a-C 4a????O 1b-C 1b????O 1b-C 3b????O 2b-C 2b	????2.369(1) ????2.128(3) ????2.142(3) ????1.365(5) ????1.366(6) ????1.370(6) ????1.374(5) ????1.370(5) ????1.376(6) ????1.443(5) ????1.448(6) ????1.437(5) ????1.450(5) ????1.391(8) ????1.410(7) ????1.370(7)	????Cr-N 1????Cr-N 2????Cr-N 3????C 11-C 12????C 12-C 13????C 13-C 14????C 21-C 22????C 22-C 23????C 23-C 24????C 31-C 32????C 32-C 33????C 33-C 34????C 1a-C 2a????C 1b-C 2b????C 1c-C 2c	????1.990(3)?? ????2.010(3) ????1.986(3) ????1.376(6) ????1.386(7) ????1.376(6) ????1.373(7) ????1.377(8) ????1.375(7) ????1.373(7) ????1.399(7) ????1.375(7) ????1.498(7) ????1.445(9) ????1.422(10)

Table 21

Kind b	Bond distance	Kind b	Bond distance
				????O 2b-C 4b????O 1c-C 1c????O 1c-C 3c????O 2c-C 2c????O 2c-C 4c????Na-C 11????Na-C 12????Na-C 13????Na-C 14????Na-C g1 c	1.379(8) 1.392(7) 1.408(8) 1.278(9) 1.409(8) 2.967(5) 2.924(5) 3.015(5) 3.104(5) 2.788(-)	?Na…Cr ?Na-Cl ?Na-N 1?Na-O 1b?Na-O 2b?Na-O 1c?Na-O 2c	????4.108(2) ????2.896(2) ????3.098(4) ????2.454(4) ????2.483(4) ????2.629(5) ????2.408(5)

Number in a parenthesis seldom is the estimation standard deviation of last position effective digital.The mark of b atom is consistent with Fig. 1.C symbol Cgl represents that C is arranged ₁₁, C ₁₂, C ₁₃And C ₁₄The center of gravity of pentatomic ring,

Therefore this value is not listed the estimation standard deviation.The bond angle of the non-hydrogen atom in table 22 crystal (Cr (NC ₄H ₄) ₃(Cl) (O ₂C ₂H ₄(CH ₃) ₂) ₂Na) ^a

Kind b	Bond angle, degree	Kind b	Bond angle, degree
				????ClCrN 1????N1CrN 2????N1CrN 3????ClCrO 1a????N 2CrO 1a????ClCrO 2a????N 2CrO 2a????O 1aCrO 2a????CrN 1C 11????CrN 1C 14????CrN 2C 21????CrN 2C 24????CrN 3C 31????CrN 3C 34????N 1C 11C 12????C 11C 12C 13????C 12C 13C 14	?????89.1(1) ?????94.0(1) ?????93.5(1) ?????86.9(1) ?????89.4(1) ?????88.9(1) ?????85.7(1) ?????78.2(1) ????124.4(3) ????128.6(3) ????126.6(3) ????126.5(3) ????125.0(3) ????128.3+3) ????110.3(4) ????106.9(4) ????106.5(2)	????ClCrN 2????ClCrN 3????N 2CrN 3????N 1CrO 1a????N 3CrO 1a????N 1CrO 2a????N 3CrO 2a????C 11N 1C 14????C 21N 2C 24????C 31N 3C 34????CrO 1aC 1a????CrO 1aC 3a????C 1aO 1aC 3a????CrO 2aC 2a????CrO 2aC 4a????C 2aO 2aC 4a	????173.9(1) ?????94.5(1) ?????90.5(1) ????1/1.9(1) ?????93.8(1) ?????94.7(1) ????171.2(1) ????105.7(3) ????106.1(4) ????106.0(3) ????113.5(2) ????122.5(3) ????110.5(3) ????107.4(2) ????124.9(3) ????111.8(3)

Table 22 (continuing)

Kind b	Bond angle, degree	Kind b	Bond angle, degree
				????N 1C 14C 13????N 2C 21C 22????C 21C 22C 23????C 22C 23C 24????N 2C 24C 23????N 3C 31C 32????C 31C 32C 33????C 32C 33C 34????N 3C 34C 33????ClnaC g1 c????ClNaO 1b????ClNaO 2b????ClNaO 1c????ClNaO 2c????ClNaN 1????ClNaC 11????ClNaC 12????CLNaC 13	????110.6(4) ????109.7(4) ????107.4(4) ????107.1(4) ????109.7(4) ????110.3(4) ????107.064) ????106.6(4) ????110.2(4) ????83.6(-) ????89.5(1) ????156.0(1) ????108.2(1) ????84.2(1) ????61.5(1) ????73.3(2) ????100.0(2) ????104.4(2)	????C 1bO 1bC 3b????C 2bO 2bC 4b????C 1cO 1cC 3c????C 2cO 2cC 4c????O aC 1aC 2a????O 2aC 2aC 2a????O 1bC 1bC 2b????O 2bC 2bC 1b????O 1cC 1cC 2c????O 2cC 2cC 1c????C g1NaO 1b C????C g1NaO 2b C????C g1NaO 1c C????C g1NaO 2c????O 1bNaO 2b????O 2bNaO 1c????O 1bNaO 2c????O 2bNaO 1c	?????114.7(4) ?????115.6(5) ?????114.2(5) ?????116.(5) ????105.8(3) ????109.8(4) ????112.8(5) ????112.6(5) ????114.9(6) ????121.1(6) ????111.1(-) ????110.2(-) ?????99.4(-) ????155.9(-) ?????67.4(2) ????146.4(2) ?????89.4(2) ?????89.3(2)

Table 22 (continuing)

Kind b	Bond angle, degree	Kind b	Bond angle, degree
				????ClNaC 14????N 1NaC 11????N 1NaC 14????C 11NaC 12????C 12NaC 13????C 13NaC 14	????81.1(2) ????25.9(2) ????25.5(2) ????27.0(2) ????26.9(2) ????25.9(2)	????O 2bNaO 2c????O 1cNaO 2c????N 1NaC 12????N 1NaC 13????C 11NaC 13????C 12NaC 14????C 11NaC 14	????88.8(2) ????65.1(2) ????43.8(2) ????43.2(2) ????43.5(2) ????42.9(2) ????41.9(2)

Numeral in a parenthesis is the estimation standard deviation of last position effective digital.

The mark of b atom is consistent with Fig. 1.

C symbol Cgl represents to contain N ₁, C ₁₁, C ₁₂, C ₁₂And C ₁₄Wuyuan

The center of gravity of ring therefore should the unlisted estimation standard deviation of value.

In order describing the present invention have been done detailed description, can not to have thought that the present invention is only limited to these, the present invention also is included in all changes and the remodeling in its spirit and scope.

Claims (20)

1. make the method for olefinic polymerization in the presence of a kind of catalyzer, this catalyzer is to comprise that by generation the mixture of following component prepares:

(a) a kind of chromic salts;

(b) a kind of metal amide; With

(c) a kind of electron pair donor(EPD) solvent.

2. make alkene trimeric method in the presence of a kind of catalyzer, this catalyzer is to comprise that by generation the mixture of following component prepares:

(a) a kind of chromic salts;

(b) a kind of metal amide; With

(c) a kind of electron pair donor(EPD) solvent.

3. make the method for olefinic polymerization in the presence of a kind of catalyzer, this catalyzer is to be prepared by the method that comprises the steps:

(a) mixture of generation chromic salts, metal amide and electron pair donor(EPD) solvent;

(b) from the mixture of (a), reclaim a kind of chromium cpd that contains; With

(c) make containing chromium cpd and a kind ofly being selected from metal alkylide and lewis acidic activating compounds reacts to generate a kind of reaction product of (b).

4. according to the method for claim 3, wherein the Preparation of catalysts method also comprises the steps:

(c) a kind of inorganic oxide is added in the reaction product of (b);

(d) reclaim solid product.

5. make alkene trimeric method in the presence of a kind of catalyzer, this catalyzer is to be prepared by the method that comprises the steps:

(a) mixture of generation chromic salts, metal amide and electron pair donor(EPD) solvent;

(b) from the mixture of (a), reclaim a kind of chromium cpd that contains; With

(c) make containing chromium cpd and a kind ofly being selected from metal alkylide and lewis acidic activating compounds reacts to generate a kind of reaction product of (b).

6. according to the method for claim 5, wherein the Preparation of catalysts method also comprises the steps:

(c) a kind of inorganic oxide is added in the reaction product of (b);

(d) reclaim solid product.

7. make the method for olefinic polymerization in the presence of a kind of catalyzer, this catalyzer is to be prepared by the method that comprises the steps:

(a) mixture of generation chromic salts, metal amide and electron pair donor(EPD) solvent;

(b) a kind of inorganic oxide is added in the mixture of (a) to generate slurry;

(c) be selected from the slurry that metal alkylide and lewis acidic activating compounds add (b) a kind of;

(d) reclaim a kind of solid product.

8. make alkene trimeric method in the presence of a kind of catalyzer, this catalyzer is to be prepared by the method that comprises the steps:

(a) mixture of generation chromic salts, metal amide and electron pair donor(EPD) solvent;

(b) a kind of inorganic oxide is added in the mixture of (a) to generate slurry;

(c) be selected from the slurry that metal alkylide and lewis acidic activating compounds add (b) a kind of;

(d) reclaim a kind of solid product.

9. according to the described method of claim 1-8, the mixture of the wherein said mixture that comprises chromic salts, metal amide and electron pair donor(EPD) solvent for forming by 1 mole of chromous chloride, 2 moles of pyrrolesization sodium and tetrahydrofuran (THF).

10. according to the described method of claim 1-8, the mixture of the wherein said mixture that comprises chromic salts, metal amide and electron pair donor(EPD) solvent for forming by 1 mole of chromous chloride, excessive pyrrolesization sodium and excessive tetrahydrofuran (THF).

11. according to the described method of claim 1-8, the wherein said mixture of mixture that comprises chromic salts, metal amide and electron pair donor(EPD) solvent for forming by 1 mole of chromium chloride, 3 moles of pyrrolesization sodium and excessive glycol dimethyl ether.

12. according to the described method of claim 1-8, the mixture of the wherein said mixture that comprises chromic salts, metal amide and electron pair donor(EPD) solvent for forming by 1 mole of chromous chloride, excessive dimethyl pyrrole sodium and excessive tetrahydrofuran (THF).

13. according to the described method of claim 3-8, wherein said metal alkylide is a trialkyl aluminium compound.

14. method according to claim 13, wherein said trialkyl aluminium compound are triethyl aluminum.

15. according to the described method of claim 3-8, wherein said inorganic oxide is an aluminum phosphate.

16. method according to claim 1, wherein step (c) comprises and makes containing chromium cpd and a kind of aromatic substance and being selected from metal alkylide and lewis acidic activating compounds reaction of (b), with the formation reaction product.

17. according to claim 1,3,4 or 7 described methods, wherein said alkene per molecule contains 2-28 carbon atom.

18. method according to claim 17, wherein said alkene are ethene.

19. according to claim 2,5,6 or 8 described methods, wherein said alkene per molecule contains 2-30 carbon atom.

20. method according to claim 19, wherein said alkene are ethene.

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