CZ392890A3 - Polymerization process of olefins - Google Patents

Abstract

Olefin polymerisation process using a catalyst and a co-catalyst is characterised in that the co-catalyst is prepd. by reacting a mixt. of a Cr salt, a metal halide and an ether. Catalyst is esp. a supported Cr- or Ti-contg. catalyst, while the co-catalyst is esp. selected from Cr5(C4H4N)10(C4H8O)4; Cr(C4H4N)4; (Cr(C4H4N)4 (Na)2' 2(OC4H8); (Cr(C4H4N)5(OC4H8)); (Cr(C4H4N)5(OC4H8)) (Na)2 4(OC4H8) and mixts. of these, esp. supported on an inorganic oxide. 2-30C olefins may be used in the process, esp. ethylene, propylene, 1-butene, and or 1-hexene, most prefd. being a predominantely ethylene feed,. giving a prod. of density 0.9-0.93 g/ml. The process is pref. performed at 66-110 deg. C as a slurry polymerisation, and in the presence of H2 as accelerator.

Description

Field of the Invention

The invention relates to a process for the polymerization of olefins, such as ethylene, in the presence of any polymerization catalyst and one or more new chromium cocatalysts.

BACKGROUND OF THE INVENTION

It is well known that olefins such as ethylene can be polymerized using catalyst systems containing chromium-based supported catalysts or magnesium / titanium-based catalysts. Originally, these catalysts were used primarily for the production of olefin homopolymers. However, it soon became apparent that in many applications polymers having a higher impact strength than homopolymers of olefins were required. Therefore, comonomers such as propylene, butene, hexene or higher olefins have been used to produce polymers with short side chains (branches) that resemble more flexible polyolefins produced by radical polymerization. By copolymerizing these comonomers with the main olefin monomer, it is possible to make tailored resins for specific end uses. However, the production of copolymers is more costly because it is necessary to maintain a stock of different monomers and, moreover, comonomers are usually more expensive than conventional short chain monomers such as ethylene or propylene. Linear polymers of olefins, such as ethylene, with short side chains (branches) can be produced from pure ethylene feedstocks using an old radical .... ηmuxkA ηo + iT-tt-i ie rap rap rap rap ři ie ie ie ie ie ie that it is not competitive in the market.

It also appears desirable to have an additional possibility of controlling the polymerization process and the resulting polymer. Processes to further reduce the density of linear polyolefins and to allow more efficient production of comonomers and their introduction into linear polyolefins can be described as economically advantageous. From an economic standpoint, shifting the branching distribution of the polymer in terms of shortening the side chains and increasing their number is also advantageous.

The tasks solved by the invention and the means for solving them can be briefly characterized as follows:

SUMMARY OF THE INVENTION It is an object of the present invention to provide an inexpensive process for the production of linear polyolefins to which the short side chains impart rigidity.

It is also an object of the present invention to provide a process by which olefin polymers having the characteristics of copolymers can be produced from a purely monolefin feedstock.

Another object of the invention is to improve the polymerization process at all.

It is yet another object of the present invention to provide a novel polymerization process to control polymer density.

Another object of the present invention is to provide a novel polymerization process which improves the production of comonomer and its introduction into olefin polymers.

It is also an object of the present invention to provide a novel polymerization process allowing the shift of olefin distribution.

Finally, it is a further object of the present invention to provide a polymerization process which enables the control of short branches of a polymer.

SUMMARY OF THE INVENTION

The present invention relates to a process for the polymerization of olefins, characterized in that the polymerization is carried out in the presence of a polymerization catalyst and a cocatalyst prepared by a process comprising forming a mixture of a) a chromium salt, b) a metal amide and c) ether. a chromium supported catalyst or a catalyst comprising titanium and / or vanadium.

The preferred cocatalyst is used chromium compound selected from the group consisting of the compounds of the formula Cr ₅ (C ₄ H ₄ N) ₁₀ (C ₄ H _g O) ₄ Cr (C ₄ H ₄ N) _4, [Cr (C ₄ H ₄ N) ₄ ] [Na] ₂ .2 (OC ₄ H ₈ ), [Cr (C ₄ H ₄ N) ₅ (OC ₄ H 8)], [Cr (C ₄ H ₄ N) ₅ (OC ₄ H) ₈ )] [Na] ₂ ' ⁴ (° ^C 4 ^H 8) or mixtures thereof.

The cocatalyst may preferably be supported on an inorganic oxide carrier.

Particularly suitable for the process according to the invention are olefins having 2 to 30 carbon atoms per molecule, in particular ethylene, propylene, 1-butene, 1-hexene and mixtures thereof. Often ethylene is often used as the olefin.

The polymerization temperature is preferably in the range of 66 ° C to 110 ° C and hydrogen may be present in the reaction mixture during the polymerization. Preferably, the polymerization is carried out by a slurry process.

In a specific preferred embodiment of the process according to the invention, ethylene is used as the olefin and the polymer is isolated at a density of 0.9 to 0.93 g.cm &^lt; ³ & gt ^; .

BRIEF DESCRIPTION OF THE DRAWINGS FIG

Fig. 1 is a computer projection of a simplified spatial structural model or formula of the product I Cr ₅ (NC ₄ H ₄ ) _lo (OC ₄ Hg) ₄ designed by X-ray crystallography using single crystals of the compound.

Fig. 2 shows another projection of the spatial structural model of the same molecule as in Fig. 1.

Fig. 3 shows a computer-generated structure simplifying a product III molecule of the chemical formula Cr (NC.H.) _X based on data

X-ray crystallography using a single crystal of this material.

Fig. 4 shows another simplified structural representation of the same molecule as in Fig. 3; in this case it is shown a crystal structure or lattice of the formula Cr (NC.Hl) At _about .2 0C H _o.

4 2 4 o

Figure 5 is a computer-generated structure depicting, in a simplified manner, the product IV of the chemical formula Cr (NC? H?)?

Fig. 6 shows a further simplified structural representation of the same compound as in Fig. 5, but in this case the overall crystal structure or lattice of the formula (Cr (NC ^ H ^) (ΟΟ ^ Ηθ)] [Na] _{2 is shown} . 4 (OC ₄ H ₈ ).

The chromium compounds of the invention may be used either as such or supported on an Afeo cocatalyst carrier in combination with any other olefin polymerization catalyst. These polymerization catalysts. Typically, the catalysts are chromium-based catalysts (also known as Phillips catalysts) or titanium and / or vanadium catalysts.

Any of the chromium catalysts known in the art may be used. Examples of chromium catalysts include those described in U.S. Patents 4 3,887,494, 3,900,457, 4,053,436, 4,151,122,

294,724, 4,392,990 and 4,440,501.

Any catalyst known in the art can be used as the titanium and / or vanadium catalysts. Examples are the catalysts based on the magnesium / titanium combination described in U.S. Pat. Nos. 4,394,291, 4,326,988 and 4,347,158.

The chromium compounds of the invention can be used as a cocatalyst in any amount sufficient to form a comonomer that can be introduced into the polymer product.

The chromium compounds according to the invention, which can be used preferably for the trimerization of olefins and optionally also for the polymerization of olefins, can be prepared from a reaction mixture comprising a chromium salt, a metal amide and an ether. In this specification, the chromium compounds of the invention are referred to by several interchangeable names, such as chromium compounds, chromium complexes, chrompyrrole complexes and / or chromium pyrrolides.

As the chromium salt, one or more organic or inorganic salts may be used in which the chromium in the oxidation state is in the range of 0 to 6.

This definition of chromium salts also includes metallic chromium. Chromium salts can generally be characterized by the general formula GrX _n , where X is any organic or

X is an inorganic radical, wherein the individual radicals X are the same or different, and n represents an integer having a value of 1 to

6. The organic radicals may contain (ss 1 to 4 to 20 carbon atoms) and are selected from alkoxy, ester, keto and / or amido groups. The organic radicals may be straight or branched chain and may be cyclic or acyclic, aromatic. or aliphatic.

It may also be a mixture of aliphatic, aromatic and / or cycloaliphatic groups. Examples of inorganic residues include, but are not limited to, halides, sulphates and / or oxides.

Preferred chromium salts are halides such as chromium bromide, chromium bromide, chromium iodide, chromium iodide, chromium fluoride, chromium fluoride 1, chromium chromium, chromium chloride, and mixtures thereof. The most preferred chromium salts are chlorides such as chromium (III) chloride and / or chromium (III) chloride, since by-products such as sodium chloride are simply removed when used and are relatively inexpensive.

Any metal amide which reacts with a chromium salt to form a chromium-amide complex can be used as the metal amide. In general, the metal amide may be any heteroleptic or homoleptic complex or metal salt with an amide residue formed by any nitrogen-containing residue.

The metal oxide typically contains [alpha] 1 to about 20 carbon atoms.

Examples of metal amides include, but are not limited to, any amides derived from primary and / or secondary amines and alkali metals and / or alkaline earth metals (i.e., Group IA and Group IIA of the Periodic Table). The hydrocarbon residue of the metal amide salt is selected from the group consisting of straight or branched chain groups. They may be cyclic or acyclic, aromatic or aliphatic residues or mixtures of two or more thereof. Preferably, the metal amide is selected from the group of amides of elements classified in Group IA of the Periodic Table or IIA of the Periodic Table, since they readily react with chromium halides.

Examples of preferred metal amides include, but are not limited to, lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, lithium dicyclohexylamide, sodium bis (trimethylsilyl) amide, sodium indolide, sodium pyrrolide, and mixtures of two or more thereof. substances. Of the metal amides, sodium pyrrolidide, lithium pyrrolidide and / or substituted pyrrolides are most preferred because they exhibit high reactivity to other reactants, as an example. substituted, but not limited to, sodium 2,5- (3-methylpyrrolidone) and / or

3,4-dimethylpyrrolid.

As the ether, one or more ether compounds allowing the reaction between the chromium compound and the metal amide can be used in the reaction mixture. Without being bound by theory, it is believed that the ether may be both a reaction solvent and a possible reactant. As the ether, any aliphatic and / or aromatic compound containing a functional group R-O-R may be used, wherein the R groups may be the same or different, but are preferably not hydrogen atoms. Preferred ethers are aliphatic ethers with respect to safety, since aromatic ethers are toxic to humans. In addition, ethers are preferred for facilitating the reaction between the chromium halide and the metal pyrrolidide of Group IA or IIA and which can also be easily removed from the reaction mixture. Non-limiting examples of such compounds include tetrahydrofuran, dioxane, diethyl ether, dimethoxyethane (glyme), diglyme, triglyme, and mixtures of two or more thereof. Most preferred are tetrahydrofuran, tetrahydrofuran derivatives, dimethoxyethane, dimethoxyethane derivatives and mixtures thereof for the above reasons and also because the preferred amine salts are soluble in these ethers.

The amount of each of the reactants used to prepare one or more new chromium compounds may vary depending on which chromium compound is desired as the product. Thus, any number of reactants can be used to produce a particular product. Different chromium compounds can be obtained at different stoichiometric ratios. For example, by reacting about one mole of divalent chromium salt with about two moles of sodium pyrrolides, a different product may be obtained than by reacting about one mole of chromium salt with an excess of sodium pyrrolides. In addition, as mentioned above, when different, although similar components, are selected, different products can be obtained. For example, using a tetrahydrofuran or dimethoxyethane can produce a different reaction product.

12. The three reactants may be mixed in any manner under conditions suitable to obtain a solution containing one or more of the chromium compounds of the invention. The reaction is preferably carried out in the absence of oxygen, i.e. under an inert atmosphere such as nitrogen and / or argon. The reaction may be carried out at any pressure sufficient to maintain the reactants in a liquid state. Typically, a suitable pressure is in the range of from atmospheric pressure to 300 bar. For simplicity, atmospheric pressure is usually used.

The reaction temperature is any temperature at which the ethers are kept in liquid form. For the reaction to proceed more efficiently, temperatures near the boiling point of the ether used are preferred. Most preferably, the reaction is carried out at the reflux temperature of the ether by refluxing the reaction mixture for some time.

The reaction time is the time required for the reaction to proceed. This period can be any. Depending on the reactants and reaction temperature and pressure

And the reaction time will vary from psy | 1 minute to ias | 1 week. Typically, the reaction time ranges from ps 3 to 3 hours. Under optimal conditions, the reaction time may range from 3 to tas-48 hours.

When the reaction is complete, the solid reaction product can be isolated by any method known in the art

- 13 in this field. While this is not unavoidable, it is preferable to first filter the reaction mixture to remove any possible by-products, such as salts, such as sodium chloride. Only then is further processing carried out. Although the removal of any by-products is not necessary, it is preferably carried out in order to facilitate further purification of the chromium product. An example of one method of recovering the solid product from the reaction mixture after filtration is to remove excess ether. Excess ether can be removed by any method known in the art. Non-limiting examples of suitable methods for removing excess ether include slow evaporation, vacuum evaporation, and / or nitrogen purge.

Other methods of ether removal may be used alone or in combination. For example, the reaction mixture may be filtered and then dried under vacuum. Preferably when the reaction mixture is slowly heated to a temperature in the range from fRsi 10-300 ° C, preferably from 25 to "a-Si ¹ 200 ° C, for sure under vacuum and kept at this temperature. The resulting solid reaction product consists of one or more of the chromium compounds of the invention.

- 14- -

Alternatively, the reaction mixture may be filtered to remove any solid by-products and the filtered reaction mixture may be contacted with a non-polar organic solvent. The addition of a non-polar organic solvent results in one or more chromium compounds forming a solid precipitate.

Examples of non-polar organic solvents include, but are not limited to, pentane, hexane, cyclohexane, heptane, and mixtures thereof. Preferably pentane is used for this purpose since it is readily available and easy to work with.

The precipitated chromium compounds of the invention can be isolated by any method known in the art. The simplest procedure for isolating the precipitated chromium compounds of the invention is by filtration.

The reaction mixture / resulting solid reaction products are, as already mentioned, always stored under an oxygen-free atmosphere. Due to the availability and the simplicity of the embodiment, the absence of oxygen is ensured by means of an inert atmosphere such as nitrogen.

Numerous chromium compounds can be prepared by the process of the invention by varying the reactants and / or the amounts thereof. The isolated novel chromium compounds or isolated novel chromium compounds can be used in the trimerization of olefins and / or polymerization of olefins without further purification.

Optionally, the chromium compounds are purified by any methods known in the art. For example, one of the simplest purification procedures is to wash the solid obtained with a non-polar organic solvent such as toluene. For best results, non-polar aliphatic organic solvents may preferably be used. Non-limiting examples of wash solvents include pentane, hexane, cyclohexane, heptane, and mixtures thereof. Of the washing solvents, pentane is most preferred.

The chromium compounds of the invention can be used as carrier and / or non-carrier catalysts for the trimerization and / or polymerization of olefins. Chromium-based supported catalysts can be prepared by any of the methods known in the art. All supports that are useful as chromium catalyst supports can be used. Non-limiting examples of suitable carriers include inorganic oxides used alone or in combination, phosphated inorganic oxides and mixtures thereof. Particularly preferred among these carriers are silica, silica-alumina, alurain, fluoridated alumina, silanized alumina, silica, aluminophosphates, aluminum phosphate, phosphated silica, phosphated alumina, a mixture of silica and titanium dioxide, together the precipitated silica-titanium product and mixtures thereof. Currently, fluoride and silanized alumina are preferred, but any other carrier that may contain chromium may also be used. The most preferred carrier is aluminophosphate in the present view because it exhibits the highest trimerization activity (see U.S. Patent 3,364,855 (1982)).

The chromium-based supported catalyst system can be prepared by any method known in the art. For example, the reaction mixture, which is preferably pre-filtered to remove all of the particulate by-product reaction products, and which contains one or more new chrompyrrolidide compounds, may be mixed and thoroughly mixed with the catalyst support. Excess electron donor solvent such as ether may not be removed prior to contacting the catalyst support. Alternatively, the solid chrompyrrolidine compound can be redissolved _in ether. A solution of chrompyrrolide in ether usually has a blue or blue-green color, although another color can sometimes be observed.

The catalyst support is usually insoluble in a solution of the chrompyrrolidone complex in ether. The contacting may use chrompyrrolides in any excess relative to the catalyst support. Usually, however, it is sufficient to use at least 5 g of the chrompyrrolidine compound per g

- 1Z catalyst support. Preferably, 0.001 to 1 g of the chrompyrrolidine compound per g of support is used, and most preferably 40.01 to 0.5 g of chrompyrrolidine per g of support are used to achieve the best supported catalyst support and the most efficient use of reagents. The mixture can be contacted and stirred at any time at any temperature and pressure to bring the chrompyrrolidone compound into intimate contact with the carrier. For the sake of simplicity, it is preferred to operate at ambient temperature and pressure. The mixing time may be up to lael 24 hours, preferably from 5 seconds to 10 hours, and most preferably from 5 seconds to θ hours. Longer times usually do not provide any additional benefits and shorter times may be insufficient for in-depth contact »»

After addition of the carrier and thorough mixing with the chromium pyrrolide, the product is filtered off, dried under vacuum, then a solution of one or more Lewis acids preferably in a hydrocarbon solvent is added to the mixture of carrier and chrompyrrolides. For the purposes of this disclosure, a Lewis acid is defined as any electron acceptor compound. Non-limiting examples of Lewis acids include alkyl aluminum compounds, alkyl aluminum derivatives, halogenated alkyl aluminum compounds, and mixtures thereof. Non-limiting examples of such compounds include _x triethyl aluminum, diethyl aluminum,

-18 ethylaluminum sesquichloride and mixtures thereof. The most preferred aluminum alkyl compound is triethyl aluminum since it provides the catalyst with the best activity.

Any hydrocarbon that dissolves Lewis acids can be used as the hydrocarbon solvent. Non-limiting examples of hydrocarbons include aromatic compounds containing from 6 to 6 carbon atoms per molecule. Pholene is the most preferred hydrocarbon solvent, since it is readily removed and minimally interferes with the resulting catalyst.

Any amount of Lewis acid capable of activating and / or reacting with the chrompyrrolidide catalyst can be used to activate and / or react with the chrompyrrolidide catalyst. Usually about 200 moles of Lewis acid per gram of chromium are used. Preferably p-sdj 1 to part 6 is used. 100 g Lewis acid per gram of chrompyrrolid. In order to obtain the best catalyst activity, it is most preferred to use Lewis acids in an amount of x

- 13 from drawn 5 to a brightness of ϋ 30 g per gram of chrompyrrolidide. However, the amount of Lewis acid used may vary depending upon the catalytic support used. For example, when silica and / or alumina are used as carriers, too much Lewis acid may result in a decrease in catalyst activity. Conversely, the high amount of Lewis acid used in conjunction with an aluminophosphate carrier does not always result in a substantial decrease in catalyst activity.

As mentioned pyrrolide, catalyst support & Lewis to a II / n »bo - £ ikoa ^and, hereby always under dry inert-Al mixture chroraýseliay together mu atmo sférou.Během for clocking can be any pressure for simplicity working at atmospheric pressure is preferred.

With respect to temperature, the contacting can be carried out at any temperature, for convenience, working at room or ambient temperature is preferred. Care should be taken during mixing to avoid damaging the physical integrity of the chrompyrrolid, the catalyst support and the resulting supported catalyst. The components of the ternary mixture may be contacted with each other for any period of time sufficient to prepare and activate the chromium catalyst. A period of from 1 minute to 1 week is usually sufficient.

Preference is given to times ranging from canine. 30 minutes to 24 hours and the most preferred time is in the range of from 1 hour to 1 hour. 12 hours. Too short a mixing time may result in insufficient contact between the components and a too long mixing time does not add any benefit in terms of catalyst quality.

An alternative currently preferred supported catalyst production method is to mix at least one solid chrompyrrolidine compound of the invention with the hydrocarbon solvent mentioned above, such as toluene and Lewis acid, as described above, for example triethyl PVC in aluminum. The mixture may be stirred (any time that is sufficient to dissolve the chrompyrrolidone compound.

The pressure and temperature for this operation can be of any value. Usually a period of time ranging from 1 minute to &lt; 1 week, preferably from 1 hour to 24 hours and most preferably from < 3 hours to 12 hours is used. The obtained solution is brown in color.

After sufficient mixing, the carrier is added to the solution and mixed to bring the carrier into intimate contact with the solution. The carrier is used in any amount capable of carrying the chrompyrrolidone compound. Usually, the amount of carrier required is the same as the one exemplified above, as an alternative to the preparation. Any pressure and temperature can be operated, although ambient temperature and pressure are preferred for ease of use. The mixing and / or contacting time is in the range of from about 1 hour to about 1 week, preferably from about 3 hours to about 48 hours. The most preferred mixing and / or contacting time ranges from 5 hours to tfr &lt; 24 hours. At this time, maximum efficiency is achieved and a thoroughly contacted carrier is obtained.

The solution can then be filtered to obtain a solid catalyst product. Like the reactants and reaction mixtures, the catalyst product is preferably maintained under an inert atmosphere in order to maintain it as chemical stability.

When a chromium compound itself, such as chrompyrrolidone, is isolated and is to be used without support as a trimfusion and / or polymerization catalyst, trimerization or polymerization of olefins is performed in a homogeneous environment in the presence of at least one of the chromium compounds of the invention, a saturated hydrocarbon , such as diluents, and Lewis acids. Alternatively, hydrogen may also be introduced into the reactor to accelerate the reaction.

As reagents for use

When polymerized in the presence of the catalysts of the invention, X is formed

22 may use olefinic compounds which are capable of polymerization, i.e., reaction with themselves or with other olefinic compounds. The catalysts of the present invention can be used to polymerize at least one linear or branched mono-1-olefin containing from about 2 to about 8 carbon atoms. Non-limiting examples of these compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,

1-octene and mixtures thereof.

Reagents useful in the trimerization process of the present invention include a combination of any) three olefins which can a) react with themselves, i.e., which can trimerize to produce useful products (for example, the ethylene autoreactivity, which hexene), b) react with other olefinic compounds, i.e., which can co-rerotize to form useful products. For example, co-dimerization of ethylene and hexene can yield one molecule of decene and / or 1-tetradecene, co-dimerization of ethylene and Γ-butene can be obtained by octene, and co-dimerization of 1-decene and ethylene can yield 1-tetradecene and / or 1-docosene. The term trimerization as used in this specification is intended to include the co-ordination as defined above.

Suitable trimerizable olefinic compounds are _x compounds containing from about 1 to about 30 carbon atoms in the molecule having at least one

- 23 double bond. Non-limiting examples of such compounds include acyclic and cyclic olefins such as ethylene, propylene, 1-butene, 2-butene, isobutylene,

1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene,

2-heptene, 3-heptene, four normal octenes, four normal nonenes and mixtures of two or more thereof. Using branched and / or cyclic olefins as reagents, trimerization can be prevented by steric hindrance. Therefore, the branched and / or cyclic portions of the olefin molecule should be separated from the carbon-carbon double bond. The foregoing theory silent for the invention limiting character.

Reaction products, i.e. trimers and / or polymers, can be prepared using the solution, suspension and / or gas phase process using conventional catalyst systems of the invention using conventional contacting techniques and equipment. The contacting of the monomer (s) with the catalyst system can be carried out by any method known in the art of solid catalyst catalyst processes. One convenient method is to suspend the catalyst system in an organic medium and mix the resulting mixture to maintain the catalyst system. during the trimerization and / or polymerization process in suspension. Other contacting methods may also be used, such as contacting the fluidized bed, the gravity bed, and the fixed bed. Hydrogen can also optionally be introduced into the reactor to accelerate the reaction.

The catalyst systems of the invention are particularly suitable for use in suspension trimerization and / or polymerization. The suspension process is usually carried out in an inert diluent (medium) such as paraffin, cycloparaffin or an aromatic hydrocarbon. An example of one reaction diluent is isobutene. When predominantly ethylene is used as the reagent, the reaction is carried out at a temperature in the range of 50 ° C. 60 to bp · 110 ° C.

The olefinic and / or polymeric products of the invention are useful in a variety of applications. For example, they can be used as monomers in the preparation of homopolymers, copolyroers and / or terpolymers. The polymer products prepared according to the invention find wide application in a variety of applications where, for example, polyethylene is used.

The invention is illustrated by the following examples. The examples are illustrative only and do not limit the scope of the invention in any way

- 25 Examples of 'Vij hc \ & e.2, <4

Preparation of chromium containing compounds

Handling of all reagents is carried out either in a dry cabinet under a nitrogen atmosphere or in a glass apparatus under vacuum or under nitrogen. Tetrahydrofuran (THF), toluene, benzene, diethylbenzene (Aldrich, 1,2-, 1,3- and 1,4-isoraer mixture) and pentane were purified by distillation over sodium benzophenone ketyl. under nitrogen and then nitrogen was bubbled through. Dimethoxyethane (DME) (Aldrich, anhydrous) was degassed with nitrogen purge and used without further purification. Pyrrole (Aldrich, 98%) was distilled under vacuum over sodium and then degassed by purging with nitrogen. The 2,5-dimethylpyrrole is dried over calcium sulphate and then distilled under vacuum. Sodium 2,5-dimethyl pyrrolidine (NaCl 4 H 2 N) was prepared by reacting 2,5-dimethylpyrrole with an excess of sodium (40% by weight dispersion in white spirit) in refluxing tetrahydrofuran under nitrogen. Sodium pyrrolides are prepared by reacting pyrrole with an equivalent molar amount (1: 1) of sodium hydride (Aldrich, 60% by weight in mineral oil) or sodium (40% by weight white spirit) dispersion under nitrogen in dimethoxyethane or tetrahydrofuran. ) (Aldrich, 1.0 M hexanes and 1.0 M toluene) is used without further treatment. Commercially available alumina (AlgO4) Ketjen Grade'B and silica (SiOg) Davison 952 are used as supports for catalyst preparation. Fluorinated alumina ( F / Al 2 O 4,% by weight F) is prepared by adding a solution of NH 4 HF ₂ in methanol to alumina Ketjen Grade B. Phosphated silica (P / SiO ₂ , molar ratio P / Si = 0.1) is prepared by adding 10% solution of orthophosphoric acid in methanol to essential oil Dsvison 952. The aluminophosphate (AlPO4 - aluminum orthophosphate) used in the following experiments was prepared as described in U.S. Patent No. 4,364,855 to McDaniel et al., 198 2). Activation of the support is performed as follows: 25 g of support is placed in a fritted silica glass tube, fluidized with air and calcined at 700 ° C for 3 hours. Only in the case of phosphated silica (P / SiO ₂ ) calcination is carried out at 350 ° C. The air stream is then replaced with a nitrogen stream and continued until the carrier has cooled to ambient temperature.

Chpompyrrolidide complexes are usually prepared by reacting anhydrous chromium (III) chloride or chromium (III) chloride and sodium pyrrolidide (NaCl 4 H 4 N, sometimes also abbreviated as NaPy) in refluxing tetrahydrofuran (THF). At the molar stoichiometry of 1 Cr- ₂ and ₂ NaPy, the polymeric product, product II, as the main product and the five-nuclear complex, product I having the composition (Cr ^NC ^H H^ ÍOCOCHg), as by-product, is isolated, see equation 1. using a molar excess of NaPy, the dianionic square plenary complex (KC ₄ H ₄ ) ₄ } {Na} ₂ .20C ^ Hg, product III and octahedral complex is isolated

- 27 {Cr (C ₄ H ₄ N> ₅ (OC ^ Hg))} The $ _g .4ΟΩ _Η θ _4, the product IV, see Equation 2. All products were isolated by precipitation (Product II) or crystallization (Products X , III and IV) from THF solutions, with the addition of pentane.

THF 1 CrCl ₂ reflux.fr 20 hours + ->

2NaPy nitrogen atmosphere

Cr ₅ (0 ₄ H ₄ N) ₁₀ (C ₄ H ₈ 0) ₄ pentahuclear complex (I) product I + polymer complex, (II) product II (major)

Equation 1

THF

CrCl ₂ reflux, 2 hours

NaPy nitrogen atmosphere (excess) • fcr (C ₄ H ₄ N> ₄ } INa) ₂ .2OC ₄ H ₈ square plenary Cr (II), product III (main) {0r (C ₄ H ₄ N) ₅ (0C ₄ Hg) ocphedric Cr (III), product IV (secondary)

Equation 2

- 28 Example I

For the preparation of the pentebuclear complex, product 1, (Cr ^ CNC ^ H ^) and the polymeric material, product II, chromium chloride (2.0 g / 16.3 mmol) is mixed with sodium pyrrolidine (33.7 mmol) in tetrahydrofuran and the mixture is refluxed for 20 hours. The reaction mixture is filtered through a medium porosity frit and the filtrate is used for fractional crystallization of both (Cr Cr íNN ^H ^W WW? Product I and the polymeric material, product II, by addition of pentane. The polymeric material crystallizes as a blue solid. Cr ^ NC ^ H ^) 10 ^ 4¾¼ ^ ^{in the} form of opaque dark blue-red crystals.

Analysis calculated for ^C 56 ^H 72 ^N 10 ^Cr 5 · V · Product I: C 55.62, H 6.00, N 11.5S% by weight, found: C 55.46, H 6.32, N 11.15 Analysis found for Product II, Cr 11.5, C 59.75, H 7.61, N 9.17%, varies according to precipitation conditions. X-ray analysis of the crystalline structure of product I shows that it is a pentuclear complex comprising bridged amidopyrrolyl groups, terminal amidopyrrolyl groups and tetrahydrofuran ligands (Figs. 1 and 2).

- 23 Example IX

To prepare {Cr (NC ₄ H _{4) 4}} [Na} ₂ v20C H ^ _4, Product III, and {Cr (C ₄ H ₄ N) ^ (OC ^ Hg)}} £ ILA .4OC- ₂ H _{4 g} of product IV, chromium chloride (3.0 g / 24.4 mmol) is mixed with sodium umpyrrolidone (100.9 mmol) in tetrahydrofuran and refluxed for 2 hours, see equation 2. The reaction mixture is filtered through a medium porosity frit. and the filtrate was used for fractional crystallization of both {Cr (NC ₄ H ₄ ) ₄ } Naj Na ₂ .20C ₄ Hg, product III and (Cr (C ₄ H ₄ N) ((OC ₄ H ₄ )} Na Na 3 ' _2. 40C ₄ H ₈ , product IV, with the addition of pentane First, product III crystallized as translucent orange-red crystals, and then product IV crystallized as translucent red crystals. Product IV is formed as a result of the presence of chromium (III) chloride in the chromium (II) chloride used as reagent. 5 to 10% by weight of chromium chloride.

Calcd for C 24 H 32 N 2 ^O 2θ ^Γ 2 R 2 Product III: C 56.94, K 6.32, N 11.07% by weight, found: C 57.04, H 6.30, N 10.92 % by weight. Analysis calculated for C ₄₀ H 8 N 4 O 4 CrNa ₂ , product IV: C 60.90, H 7.67, N 8.88% by weight, found: C 60.81, H 7.74, N 9.44 ·%. X-ray analysis of the crystal structure of the product ΙΓΙ ... shows

30 that is a square planar complex containing terminal amidopyrrolyl ligands (Fig. 3). X-ray analysis of the crystal structure of product IV shows that it is an octahedral complex containing terminal amidopyrrolyl and tetrahydrofuran ligands (Fig. 4).

Example III

In the preparation of the active catalyst, the reaction product obtained from sodium pyrrolidide and chromium trichloride is most preferred. Pyrrole (7.0 mL / 100.9 mmol) was stirred with NaH sodium hydride (4.2 g, 60%, 105 mmol) in dimethoxyethane at ambient temperature until bubbles evolution ceased. Chromium trichloride (5.33 g / 33.7 mmol) was added to the solution at ambient temperature. The reaction mixture was refluxed under nitrogen for 5 hours, see Equation 3. A dark green solution was formed. The solution is filtered through a medium porosity frit, the solvent is removed in vacuo and its residues evaporated under vacuum drying for 12 hours. The resulting chrompyrrolidide complex is a green solid, product V. It is used in the preparation of the active catalyst without further purification.

x

- 31 dimethoxyethane 1 CrCl, reflux, 5 hours _{+ - '-} ^; > green solid

3NaPy nitrogen atmosphere (V)

Equation 3

Example IV

All X-ray analyzes of the crystalline structure were performed on single crystals by the Crystytics Company, Lincoln, Nebraska, USA, in Examples IV, VI. the resulting analytical data and data obtained by their computer processing are given.

The crystalline structure of the composition I obtained by X-ray analysis is shown in FIGS. 1 and 2. A description of the monocrystalline sample and the method of its attachment are given below.

color: dark blue shape: rectangular parallelepiped dimensions: 0,20 x 0,48 x 0, S0 mm crystal fastening: under nitrogen atmosphere the crystal was sealed with epoxy glue in a thin-walled glass capillary.

F*-. r? r-- - r- · r-r -z. c - «* c. r - r 'c <- r r r. . <- r, p. »» F f · r · · ; r <· r. ι <r r r r r r

- 32 crystal orientation: the crystal was oriented with its longest edge almost parallel to the phi axis of the tomometer diffraction width at half height based on raster A): 0 to 38 °.

Data relating to the spatial group and the unit cell crystal group: a three-sided spatial group and the number: 'PI - Cj / (No 2) the number of computer-centered reflections used to refine the unit cell dimensions by the least squares method:

20> 25 ° C = 20+ 1 ° lattice constant with estimated standard deviation:

a = 3.0 803 (2) wt α = 85.59 (2) ° Λ = 1.407 δ (6) nm b = 0.9 825 (2) w β = 96.23 (2) ° Z = 1 c = 1.4 212 (4) nm [Α] D = 109.99 (2) ° λ = 0.071073 nm molecular weight calculated density linear absorption 1209,24 x 1,427 g.cm ⁵ · coefficient: ^3a 0,96 mm “ • 1 •

Tables I to V show the resulting parameters used to create the molecular structures shown in Figures 1 and 2.

- 33 Table I

Atomic coordinates of non-hydrogen atoms in [Cr ₅ (M0 ₄ H ₄ ) ₁₀ (OC _A ) ₄ l ^and atom type ^ fractional coordinates

10 ⁴ x 10 ⁴ y 10 ⁴ from the crystalline equivalent isotropic thermal parameter,

B, .times.10.times.10 ^c

^Cr l 0 ^u 0 0 0,25 mm (1) Cr ₂ 636 mm (1) 2281 (2) 1500 (2) 0.24 (1) ^Cr 3 -1179 841 (2) 3122 (2) 0.28 mm (1) ^K la -1155 (2) 935 (2) 715 (1) 0,25 mm (1) ^C la -2195 (3) 64 (4) 1231 (2) 0,31 mm (1) ° 2a -3313 (3) 390 (4) 965 (2) q4KD ^C 3a -3014 (3) 1486 (6) 257 mm (3) 0.43 (1) ^C 4a -1728 (3) 1791 (3) 116 mm (3) 0.34 (1) ^H lb 1566 (2) 1902 (2) 331 (2) ' 0.29 mm (1) ^C lb 1753 (3) 3095 (3) -308 (2) 0,36 mm (1) ^C 2b 3035 (4) 3751 (4) -432 (2) 0.51 (2) ^C 3b 3736 (3) 2986 (6) 131 (2) 0.51 (2) ^C 4b 2823 (3) 1865 (3) 587 (2) 0,38 mm (1) ^K le -320 (2) 2997 (2) 2480 (1) 0,27 mm (1) ^C lo 375 (3) 3732 (3) 3273 (2) 0.34 (1)

equivalent isotropic thermal parameter,

B, ^10'C

Cj "

- 9 y .9 y • y <

- 3f Table I - continued Atom type * ³ Fractional coordinates 10 ⁴ x 10 ⁴ y 10 ⁴ z

^C 2o 29 (5) 4919 (3) ° 30 - 908 4967 (3) ^C 4c -1105 (3) 3809 (3) ^N ia 443 (2) 350 (2) ° ia 1600 (3) 715 (3) ^c 2a 2321 (3) -133 (4) ^c 3a 1567 (6) -1070 (4) ^c 4a 422 (3) -763 (3) ^N le -1972 (2) -1122 (2) ° le -1344 (6) -2107 (3) ^C 2e -2189 (6) -3307 (3) ^C 3e -3361 (4) -3061 (3) ^C 4e -3206 (6) -1731 (3) ° lf 2351 (2) 3985 (2) ^C lf 3536 (3) 4018 (3) ^C 2f 4470 (5) 5479 (5) ^C 3f 3642 (6) 6408 (4) ° 4f 2396 (3) 5463 (3)

3383 (2) 0.43 (1) 263K3) 0.42 (1) 2101 (2) Q32 (l) 2743 (1) 0.28 mm (1) 3289 (2) 0,36 mm (1) 3102 (2) 0.48 (2) 2403 (2) 0.46 (2) 2203 (2) 36) 36 (2) 3801 (1) 0,35 mm (1) 4069 (2) 0.41 (1) 4503 (2) 0.44 (1) 4531 (2) 0.47 (1) 4097 (2) 0.47 (1) 1883 (1) 0,32 mm (1) 2483 (2) 0.43 (1) 2336 (4) 0.76 (2) 2147 (3) 0,62 mm (2) 1635 (2) 0.40 (1)

r f. ; e., C e C j \ r j · r * “r. <\, * r e. r - »Γ C r

- 35 Table I - continued

atom type ^ Fractional 10 ⁴ x 10 ^4-ordinate Y 3 10 ⁴ Z isotropic equivalent thermal parameter, Β, x 10 ^c ° lg -2551 (2) 1543 (2) 3659 (1) Q35 (l) ^c ig -3763 (3) 1733 (6) 3232 (2) Q44 (l) ^C 2g -4097 (4) 2625 (7) 3907 (3) 0 _r 57 (1) ° 3g -3524 (6) 2241 (5) 4845 (2) 0.57 (2) ^C 4g -2319 (6) 1977 (5) 4633 (2) 0.50 (2)

Comment:

and The number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

The atoms are labeled in accordance with FIG.

c This is one third of the foot of the orthogonal tensor Bij.

d This is the value required due to symmetry and is therefore given without the estimated standard deviation.

• r &

f * Ir -> r c f f · r λ r - r

C s * · r r

- 36 Table II

Anisotropic thermal parameters of non-hydrogen atoms in crystalline ECr (íNC ^H ^) ^ (OC ^Hg) ^] ^{a, b} • 2 type Anisotropic thermal parameter ( ^nnr > XlC?

atom ^{0 B} ii ^B 22 ^B 33 ^B tt2 ^B 13. ^B 23 ^Cr l 0.20 (1) 0,23 mm (1) 0,32 mm (1) 0/1 5 (1) 0.05 (1) -0.04 (1) Cr ₂ 0,23 mm (1) 0.22 (1) ’ 0,27 mm (1) (her7 (l) ¢ 03 (1) -CjO2 (1) ° r ₃ 0,27 mm (1) ¢ 25 (1) 0.34 (1) 0.11 (1) 0,08 mm (1) ο, οκι) ^K la 0,21 mm (1) 0,27 mm (1) 0.29 mm (1) 08, 08 (2) 01.02 (1) -0.02 (1) ^C la 0.28 (2) 0,31 mm (2) 0,30 mm (2) ¢ 04 (2) 08) 08 (1) -qo4 (i) ^C 2a 0.23 mm (2) 0.49 (2) 0.49 (2) ¢ 08 (1) ¢ 05 (1) ~ qi6 (1) ^C 3a 0,31 mm (2) 51) 51 mm (2) 0,52 mm (2) 0,22 mm (2) -0.07 (2) -0.11 (2) ° 4a 0,36 mm (2) 0,32 mm (2) 0.34 (2) ¢ 15 mm (1) -0.02 (1) - () 04 (1) ^N lb 0.24 (1) 25, 25 mm (1) 0,35 mm (1) 0,03 mm (1) C) 05 (l) -0 / 4 (1) ^C lb (40) (2) ¢ 31 mm (2) 33 ¢ 02 (2) qiKD-iqi (i) ^C 3b 0.46 (2) (42) 0.54 (2) -0.07 (2) (2) -0.05 (2) ^C 3b 0,25 mm (2) (50) (2) 0.71 (3) -0.03 (2) ¢ 15 (2) 0.27 (2f ° 4b 0.29 mm (2) 0,38 mm (2) 48) 48 mm (2) qio (D 0.00 (2) -0.15 (2) ^H lo 0.28 mm (1) 0,25 mm (1) 0,30 mm (1) Q1151) 0.03 (1) -0.02 (1) ^C lc 0,36 mm (2) (35) (2) ¢ 31 mm (2) 0,10 mm (1) 0.04 (1) -0.03 (1) ^C 2c 0,52 mm (2) 0.34 (2) 0.43 (2) ¢ 13 mm (2) 0.06 (2) -0.13 (1) ^C 3o 0.51 (2) 31 (2) 0.50 (2) 0,22 mm (2) 0.05 (2) -0.05 (2) ^C 4c 0,35 mm (2) (34) (2) 0,31 mm (2) 0.16 (1) 0.04 (1) qoid) ^H ld 0,32 mm (1) 0,23 mm (1) 31) 31 (2) 0.12 mm (1) 0.06 (1) 0.03 (1)

C.P Ρ,> · ρ yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy

- ι *

- 37 Table II - continued

atom type ⁰ Anisotropic thermal parameter (n / ftclO) ^B 11 ^B 22 ^B 33 ^B 12 ^B 13 ^B 23 ^c id 0,33 mm (2) ¢ 32 mm (2) ¢ 43 (2) ¢ 09 (2) 906 (1) -qoo (i) ^C 2d 0,36 mm (2) 0 _f 5O 0.59 (2) ¢ 24 mm (2) Ö 06 (2) Õ 11 (2) ^C 3d ¢ 61 (2) ¢ 44 mm (2) 0.47 (2) ¢ 36 mm (2) 0.11 (2) ¢ 03 (2) ^C 4d ¢ 49 mm (2) 0,35 mm (2) ¢ 31 mm (2) ¢ 23 mm (2) ¢ 04 (1) ¢ 01 (1) ^N le 0,36 mm (2) ¢ 30 mm (1) ¢ 43 (2) ¢ 13 mm (1) ¢ 14 (2) ¢ 04 (2) ^C le 0.46 (2) ¢ 36 mm (2) ¢ 46 mm (2) ¢ 20 mm (2) Ö 10 (2) Õ 06 (2) ^C 2e 0.64 (3) ¢ 30 mm (2) ¢ 37 mm (2) ¢ 15 mm (2) ¢ 07 (1) ¢ 04 (2) ^C 3e 0.55 (3) 0/31 (1) ¢ 46 mm (2) -0/01 (1) ¢ 18 (2) -0.00 (1) ^C 4e 0,35 mm (2) 0/38 (1) ¢ 62 (3) ¢ 09 (1) 0.17 (2) ~ q04 (2) ° lf 0.29 mm (1) ¢ 25 mm (1) 40 (1) ¢ 06 (2) -0 / 0K1) 0.02 (1) ^C lf 0.34 (2) Q44 (1) ¢ 45 mm (2) ¢ 09 (1) ~ <jOs (0) ~ 0/06 (0) ^C 2f 0,45 mm (3) ¢ 67 (2) ¢ 95 (3) - (? 03) -0.15 (3 ·) -0.06 (3) ^C 3f ¢ 59 mm (3) ¢ 34 mm (2) ¢ 79 (3) - <02 02 (1) -006 (3) -0.09 (1) ^C 4f 0/45 (1) ¢ 23 mm (1) ¢ 48 mm (2) ¢ 07 (2) 0,06 (2) -n) Ol (l) ° lg <7.34 (1) 0.41 (1) ¢ 37 mm (1) ¢ 19 mm (1) ¢¢ 7 (2) -001 (2) ^C lg 0/31 (1) ¢ 55 (2) 0.50 (2) ¢ 20 mm (2) /05 04 (1) -0/05 (1) ^C 2g 0.47 (3) 0,65 mm (3) ¢ 72 (2) ¢ 35 mm (2) ¢ 02 (2) -0/12 (1) ° 3g 0.60 (3) ¢ 75 mm (3) 0/50 (1) 0,36 mm (2) ¢ 16 (2) -0/08 (1) ^C 4g 0.45 (2) ¢ 77 (2) ¢, 35 mm (2) ¢ 27 mm (2) 0/08 (2) - Oct05 (2)

Comment:

(a) the number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b) The form of anisotropic thermal parameter;

- 38 T a b u 1 k and III

Atomic coordinates of hydrogen atoms in crystalline [Cr ₅ CNC ₄ H ₄ ) _lo (0C ₄ H ₈ ) ₄ ] ^and

atom type ^ 10 ⁴ x fractional coordinates 10 ⁴ z ^H la -2129 -661 1707 ^H 2a -4154 -55 1219 »3a -3608 1937 -69 ^H 4a -1267 2508 -339 ^H lb 1053 3405 -617 ^H 2b 3405 4593 -834 ^H 3b 4676 3202 189 ^K 4b 3031 1158 1020 ^H lc 1013 3445 3687 ^H 2c 364 5592 3881 ^H 3c -1331 5685 2512 ^H 4c -1704 3580 1540 ^H ld 1881 1460 3743 ^H 2d 3177 -88 3396 ^H 3d 1807 -1790 2120 ^H 4d - 291 -1252 1752 ^H le -446 -1976 3968 ^H 2e -1997 -4161 4742 ^H 3e -4139 -3699 4803

- 3 $ Table III - continued

atom type ¹³ Fractional 10 ⁴ x coordinates 10 ⁴ y 10 ⁴ z ^H 4e -3878 -1286 4012 ^H lfa 3351 3836 3136 ^H lfb 3882 3308 2299 ^H 2? A 5068 5771 2893 ^H 2fb 4965 5524 1806 ^H 3fa 3462 6711 2728 ^H 3fb 4068 7245 1757 ^H 4fa '2417 5653 964 ^H 4fb 1641 5625 1839 ^H lga -3631 2231 2623 ^H lgb -4455 813 3162 ^H 2ga -5037 2381 3901 ^H 2gb -3704 3640 3750 ^H 3ga -4129 1385 5124 ^H 3gb -3307 . 3025 5266 ^H 4ga -2173 1220 and 5050 ^H 4gb -1565 2846 4703

-40 Notes:

and the hydrogen atoms were included in the calculation of the structure factor as idealized atoms (assuming sp 2 or sp 3 hybridisation carbon atoms and CH bonds of length 0.096 nm riding ^'1 to the corresponding carbon atoms. isotropic thermal parameter of each hydrogen atom was determined as 1.2 times equivalent isotropic thermal parameter of the carbon atom to which the hydrogen atom is covalently bonded.

b Hydrogen atoms are designated with the same numerical and written subscripts as the carbon atoms to which they are bound. If necessary, an additional subscript a or b is used to distinguish between hydrogen atoms bound to the same carbon atom.

- 41 Table IV

Bonding distances of non-hydrogen atoms in crystalline [ογ ₅ (Ν0 ₄ η ₄ ) _1ο (Ο0 _Λ ) ₄ ] ⁸

type binding length, wt type ^b binding length Cr- ₂ 0.3.066 (1) ° lf “ ^C lf 0.1 451 (5) Cx * 2 * 0.3 121 (1) ° if- ^c 4f £ j'i 454 (5) -Cl lg lg 0.1 448 (6) ^Or l- ^N la 0.2 153 (3) o, -c, lg 4g £) 1,451 (5) ^Or i- ^N -ib 0.2 092 (3) ^0r 2 ^_K l _a 0.2 178 (3) ^C 1a ^C 2a I} 1,360 (6) ^Cr 2- ^K lb 0.2 149 (3) ° 2a - ^C 3a 0.1 395 (6) ^Cr 2- ^K lc 0.2 112 (4) ^C 3a ' ^C 4a Q1 351 (5) ^Cr 3- ^N lc 0.2 172 (3) ° 1b- ° 2b 0.1 338 (6) ^Cr 3 -? Ld 0 _y 2 101 (4) ^C 2b- ^C 3b 0.1 393 (7) ^Cr 3- ^K le 0.2 037 (3) ^C 3b ^C 4b 0.1 376 (6) ° lo- ° 2c 0.1 365 (7) ^Cr 2 ° lf 0.2 082 (2) ^{C 2 C-} 3e 0.1 400 (6) Cr-O3 lg 0.2 063 (3) ^C 3c- ^C 4c 0.1 356 (6) ^C 1d ^C 2d 0.1 376 (7) ^K la- ^C la '0.1 399 (4) ^C 2d ” ^C 3d «396 (6) ^H 1a- ^C 4a 0.1 397 (5) ^C 3d ” ^C 4d 0.1 367 (8) ^N lb “ ^C lb 0.1,398 (5) ^C le ^C 2e 0.1 370 (5) ^N 1b ^C 4b 0.1 379 (6) ^C 2e- ^C 3e 0.1 374 (8) ^K lc- ^C lc 0.1 388 (4) ^C 3e ' ^C 4e 0.1 366 (6)

iíit) r? c .- * r * '- r - · - r ι ~ - -, ··

Ρ ~ {, · · ρ * · 'ρ - r r f · - - f: \ ·.

ρ p - · ø r γ

- 42. Table IV - continued

binding length, npj:

binding length, nm

lc ' ^C 4c Q1 394 ld ^C ld Q1 349 (4) ^C 1f ” ^C 2f 0.1 460 (6) ld ” ^C 4d 0.1 377 (5) ^C 2f ~ ^C 3f 0.1 474 (9) le ^ le qi 370 (5) ^C 3f ^C 4f 0.1 496 (6) le ' ^C 4e íjl _; 361 (5) ^c i _g -% 0.1 496 (8) ^{C _C} 2 g 3 g 0.1 485 (7) ^C 3g ”° 4g 0.1 476 (9)

Comment:

and The number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b The atoms are labeled in accordance with Figure 1.

- 43 Table V

Coupling angles for non-hydrogen atoms in crystalline [0r ₅ (NC ₄ H ₄ ) ₁₀ (00 _4% ) .4] ⁸

type ^b (') Angle Ideg iyp ^b AND angle, Wlb 84.8 (1) ^{Cr A and Cr} 2 90.2 mm (1) Wu ^c 180.0 (-) ^d ° * A _and ^c i _a 121.2 mm (2) ^N ib ^Cr A _and ^c 95.2 mm (1) Wle 118.0 (2) ^N 1b ^Cr Ab ° 180.0 (-) ^{d Cr} 1 C _and ^C 4a 113.4 (2) ^Cr 2 ^N 1 _and ^C 4e 110.6 (2) ^H 1 _and ^Cr 2 ^N 1b 82.9 mm (1) ^C 1A and ^C 4s 103.5 (3) ^N 1 _and ^Cr 2 ^N 1c 96,5 mm (1) ^Or Ab ^Or 2 92.6 mm (1) ^N 1b ^Cr 2 ^N lc 168.9 mm (1) ^Cr Ab ^C 1b 117.9 mm (2) ^N la ^Cr 2 ° lf 162.4 mm (1) ^Cr 2 ^N 1b ^C 1b 107.6 (3) ^N 1b ^Cr 2 ° 1f 89.5 mm (1) ^Cr Ab ^C 4b 120.6 (3) 87.9 (1) ^Cr 2 ^N 1b ° 4b 113.0 (3) ^C 1b ^N 1b ^C 4b 104.4 (3) ^N lc ^Cr 3 ^K ld 88.1 mm (1) ^Cl Ae ^C 5 93,5 mm (1) ^N lc ^Or 3 ^N le 176.5 mm (1) ^Cr 2 ^N 1c ^C 1c 121,4 mm (3) ^N ld ^C 3 3 ^K le 93,5 mm (1) ^Cl AAc 100,0 / 2) ^K lc ^Cr 3% 88.8 (1) ^Cl -2 ^S 1c ° 4c 116.1 (2)

- 44 Table V - continued

type ^b (') angle, ápg type ^b ( angle, ^N ld ^Or 3 ° lg 170.4 (1) ^Cr 3 ^K lo ° 4c 121,5 mm (2) ^N le ^Or 3 ^O lg 89.1 mm (1) ^C 1c ^N 1c ^C 4c 104.2 mm (3) ^Cr 3 ^N ld ^C ld 121.3 mm (3) ^N la ^C la ^C 2s 110.6 (3) ^Cr 3 ^N ld ^C 4d 127.8 (3) ^C 1a ^C 2a ^C 3a 107.5 (4) ^C ld ^N ld ^C 4d 106.4 (4) ^C 2a ^C 3a ^C 4a 106.9 (4) ^Cr 3 ^K le ^C le 126.3 mm (3) ^C 3a ^C 4a% a 111,5 mm (3) ^Cr 3 ^K le ^C 4e 128.3 mm (3) ^N 1b ^C 1b ^C 2b 111,2 mm (4) ° le ^N le ^C 4e 105.3 mm (3) ^C 1b ^C 2b ^C 3b 107.4 (4) ^C 2b ^C 3b ^C 4b 107.0 (4) ^Cr 2 ° lf ^C lf 131,5 mm (2) ^C 3b ^C 4b ^N kb 110.1 (4) ^Cr 2 ° 1f ^C 4f 118.9 (2) ^N 1c ^C 1c ^C 2c 110.9 (4) ^C 1f ° 1f ^C 4f 109.1 mm (3) ^C 1c ^C 2c ^C 3c 106.8 (4) ^Or 3 ° lg ^C lg 131,9 mm (3) ^C 2c ^C 3c ^C 4c 107.2 mm (4) ^Or 3 ° ^C, 4 g g 118.6 (3) ⁰ 3c ° 4c ^N lo 110,9 mm (3) ^C 1g ° 1g ^C 4g 109.5 (4) ^N 1d ^C 1d ^C 2d 110.3 (4) Ld ^{C C C} 2d 3d 106.7 (4) ° 1f ^C 1f ^C 2f 105.0 (4) ^C 3d ^C 3d ^C 4d 106.6 (5) ^C 1f ^C 2f ^C 3f 104.9 (4)

- 45 Table V - continued

type ^b (’) angle deg type ^b O angle deg ^C 3d ^C 4d ^N ld 109.9 mm (3) ^C 2f ^C 3f ^C 4f 104.4 (4) he ^C le ^C 2e 110.0 (4) ^C 3f ^C 4f ° 1f 105.4 (4) ^C le ^C 2e ^C 3e 107.2 mm (4) ° 1 _g ^C 1g ^C 2g 104.8 (4) ⁰ ° 3e 2e 4e ⁰ 106.7 (4) ^C 1g ^C 2g ^C 3g 104,2 mm (5) ^C 3e ^C 4e ^N le 110.8 (5) ^C 2g ^C 3g ^C 4g 104.2 mm (4) ^C 3g ^C 4g ° lg 106.1 (4)

Comment:

and The number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b The atoms are labeled in accordance with Figure 1.

c Apostrophe-marked atoms are symmetrical to non-apostrophe atoms (-x, -y, ‘'and -z coordinates), with the fractional coordinates x, y, and z being given in Table I.

* d This is the value required due to symmetry and is therefore given without the estimated standard deviation.

Example 46

Single crystal X-ray analysis revealed the structure of Cr (NC? H?)?, Which is part of product III (see Figure 3). Further, a single crystal X-ray analysis revealed the structure of the compound having the composition [Na 2 CH 3 Cl 2 H 2 O 2] 2 (OC 4 H 8), which is the product III (see Figure 4). The description of the single crystal sample and the method of its attachment during measurement are given below:

color: red-orange shape: rectangular parallelepiped dimensions: 0.50 x 0.55 x 0.65 mm crystal fastening: the crystal was glued into a thin-walled glass capillary and the capillary was sealed under a nitrogen atmosphere.

crystal orientation: the crystal was oriented with its longest edge almost parallel to the phi axis of the diffractometer.

width at half height based on ω: 0.86 °.

Spatial group and unit cell data crystalline group: monoclinic space group and number: C2 / c - (6 · 15) number of computer-centered reflections used to refine the unit cell size by least squares:

dimensions: 15 20> 25 ° C = 20 \ + 1 ° lattice constant with estimated standard deviation:

α = 9,552 (2) rot α = 90.00 ° V = ≥ 697 (1) rw ³ b = 1.5 118 (2) ηκ β = 98.99 (1) ° Z = 4 c = 1.8 967 (3) nb) 1 3 ~ = 90.00 ° ^λ = 0/71073 n> n molecular weight: 506.52 xW xf ^ ² · ⁷

calculated density: 1.248 g / cm 2

Ra - 1 linear absorption coefficient: ^J 0.47 mm

Tables VI to X summarize the resulting parameters for the molecular structure design shown in Figures 3 and 4.

Table VI

Atomic coordinates for non-hydrogen atoms l ^Ka h {Cr (KC ₊ H ₄ ) ₄ j.20C ₄ H ₈ ) ^and fractional coordinate type ^b 10 ⁴ x 10 ⁴ y 10 ^{4 in} crystalline equivalent isotropic thermal parameter B, 10 ^c

anion Steed e ^a 2982 (2) 25OO ^d 0.50 (1) ^K 1 1901 (3) 2924 (1) 3183 (1) 0.56 (1) »2 ° ^d 4343 (2) 25OO ^d 0.52 (1) ^K 3 0 ^p 1612 (2) 2500 ^d 0.70 (2) ^C U 3241 (6) 2950 (2) 3000 (2) 0,65 mm (2)

- 48 Table VI - continued atom type fractional coordinates 10 ⁴ x 10 ⁴ y 10 ⁴ z equivalent isotropic thermal parameter B, rwx IQ ⁰

^C 12 4224 (7) 2768 (2) 3587 (2) (73) (2) ^C 13 3513 (6) 2630 (3) 4146 (2) q82 (1) ^C 14 2094 (6) 2734 (3) 3884 (2) £ 76 (2) ^C 21 987 (4) 4884 (2) 2926 (2) »(1) ° 22 582 (3) 5753 (2) 2766 (2) £ 69 (2) ^C 31 398 (6) 1081 (2) 1996 (3) 494 mm (2) ° 32 236 (6) 213 (2) cation 2189 (4) 3.33 (6) Ka 2301 (1) 6879 1783 (2) £ 69 (1)

crystallization solvent

° 1 2065 (3) 5108 (1) 830 (1) 0.83 (1) ^C 41. 2759 (12) 5174 (4) 239 (3) 3.43 (4) ° 42 2884 (12) 4319 (6) -79 (3) 3.48 (4) ° Í3 1893 (9) 3786 (4) 264 (5) 3.42 (4) ° 44 1699 (8) 4231 (3) 902 (3) 3.20 (3)

Comment:

and The number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b The atoms are labeled in accordance with Figure 1.

r, - 4S c This is one third of the trace of the orthogonalized tensor Bij.

d This is the value required due to symmetry and is therefore given without the estimated standard deviation.

Table VII

Anisotropic thermal parameters for non-hydrogen atoms in crystalline Ni} ₂ {Cr (OC ₄ H _Q ) ^a ' ^b <2,

Anisotropic thermal parameter (tv *) x10)

atom type ^{0 B} 11 ^B 22 ^B 33 ^B 12 ^B 13 ^B 23 Cr (j 63 (1) anion 034 (1) 0 * 55 (2) · o ^a 0,15 mm (1) o ^{a K} 1 0,69 mm (2) 0.44 (2) ^ 56 006 0.12 mm (1) 0,06 mm (1) n ₂ 0.64 (3) 0,39 mm (2) q56 (2) About ^d 0,16 mm (2) o ^{a K} 3 0,65 mm (3) 0,30 mm (2) 3.07 (4) o ^a 0,14 mm (3) o ^{a C} 11 0.70 (3) or 50 (2) 0.70 (3) -0.06 (2) 0.18 (2) 0,02 mm (2) ^C 12 0.70 (3) J62 (3) 84) 84 (2) 0,04 mm (2) 0,07 mm (2) - q 0 8 ^C 13 3.03 (4) 0.59 (3) 0.50 (3) 0.22 mm (3) - () 07 (3) • 0 (1) ^C 14 0,86 mm (3) 0,86 mm (3) 0.59 (3) ¢ 16 mm (3) 0,16 mm (2) 0.05 (2) ^C 21 0,66 mm (2) 0.45 (2) 0.70 (3) - 0,02 915 (1) - () 07 (2) ^C 22 0.68 (3). 0,38 mm (2) 3.05 (4) -0.07 (2) / (27) -0.09 (2) ^C 3l 065 (2) 0,61 mm (3) 3.52 (5) 06) 06 (1) 0,09 mm (3) -0.36 (3) ^C 32. 0.71 (5) 0.46 (2) ^ 66 (14) 0,06 mm (3) -0.20 (6) “0.44 (4)

c ·

- 50 Table VII - continued

atom type ⁰ Anisotropic thermal parameter (h ^ xló) ^B 23 ^B 11 ^B 22 ^B 33 ^B 12 ^B 13 On cation 0.70 (1) 0.57 (1) 81 * (1) -2 (1) 15 mm (1) -15 (

crystals to start the solvent

° 1 1,08 mm (2) 0,65 mm (2) 0,82 mm (2) - (10) (2) 38 (2) - 0,16 ( ^C 41 ^ 22 1,12 mm (5) 1.16 (5) -0.46 (5) 92 (6) - 0,22 ( ^C 42 1.92 (8) 1,60 mm (8) 1.07 (5) 0,12 mm (6) 70 (4) -0.32 ( ° 43 1.47 (6) 1.09 (6) 1.77 (8) - (27) (5) 48 (6) - () ° 44 1,77 mm (6) 0.77 (4) 1.24 (5) -0.21 (4) 76 (5) -0.14 (

Comment:

and The number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b The form of anisotropic thermal parameter. Atoms are labeled in accordance with Figs. 1 and 2.

d This is the value required for symmetry and is therefore given without the estimated && T deviation.

- 51 Table VIII

Atomic coordinates of hydrogen atoms in crystalline

[Na] ₂ {Cr (NC ₄ H ₄ ) ₄ } .2 (OC ₄ H ₈ ) ^a

atom type * ³ Fractional 10 ⁴ x coordinates 10 ⁴ y 10 ⁴ z ^H 11 anion 3456 3081 2541 ^H 12 5235 2740 3600 ^H 13 3522 2480 4620 ^H U 1341 2679 4164 ^H 21 1665 4687 3265 ^H 22 1071 6262 2985 706 1274 1565 3χ ^H 32 483 -301 1937

crystallization solvent

^K 41a. 2250 5576 -100 ^H 41b 3710 * 3389 385 ^H 42a 3756 4091 -1 ^H 42b 2464 4348 -583 ^K 43a 995 3707 -39 ^H 43b 2326 3220 377 ^H 44a 2295 3973 1304 ^H 44b 723 4191 969

- 52 Notes:

and hydrogen atoms were included in the structural factor calculation as idealized atoms (assuming sp ² • 5 or sp ^J hybridization of carbon atoms and a CH bond length of 0.096 nm ezd traveling na on the corresponding carbon atoms. The isotropic thermal parameter of each hydrogen atom 2 times the equivalent isotropic thermal parameter of the carbon atom to which the hydrogen atom is covalently bonded.

b Hydrogen atoms are designated with the same numerical and letter subscripts as the carbon atoms to which they are bound. If necessary, an additional subscript a or b is used to distinguish between hydrogen atoms bound to the same carbon atom.

c *

Γ '. and·

- 5.

Table IX

Coupling distances and angles of non-hydrogen atoms in the anion of crystalline [Na] ₂ (Cr (NC ₄ H ₄ ) ₄ ). 2 (OC ₄ Κ _θ ) ^a

type ^b binding length, nm type ^b binding length _r Mi Cr-1 0.2 057 (3) ^c n- ^c i2 0.1 355 (7) Cr-K ₂ 0.2 056 (4) ^C 12 - ^C 13 (jl 368 (9) Or-K ₃ · 0.2 072 (5) ^C 14 ^C 14 Oct 374 (9) ^C 21 ' ^C 22 Oct 372 (6) ^H i- ^C n 0.1 369 (7) Π -Γ c ^υ 22 ^υ 22 » ¢ 1,379 (9) ^K 1 ' ^C 14 0.1 344 (6) ^C 31 - ^C 32 0.1 376 (7) ^N 2 ' ^C 21 or 360 (5) ^C 32 ^C 32 ^C 0 _f l 327 (17) ^N 3- ° 31 0.1 344 (7) type ^b O angle, dag type ^b c °) angle, eg- N-jCrNg 92.5 mm (1) ^C 1 ^C 11 ^C 12 110.5 (5) ^N l ^CrK 3 87,5 mm (1) ^C 11 ^C 13 ^E 12 107.3 (5) NjCrNj., ⁰ 175.1 mm (2) ^C 12 ^C 13 ° 14 106.4 (5) N ₂ CrN ₃ 180.0 (-) ^{d C} 1 ^C 14 ^C 13 110.9 (5) • ^ 23 ^ 22 110,2 mm (4) CrN ₁ C _n 127.5 (3) ^C 21 ^C 22 ^C 22 » ^c 106.8 (3) ^OrN l ^c 14 127.1 (4) ^C 3 ^C 31 ^C 32 109.1 (6) ^C 11 ^N 1 ^C 14 104.9 (4) ^C 31 ^C 32 ^C 32 ' ^c 107,5 (4) CrNgCgl 127.0 (2) c ₂₁ n ₂ c ₂ i. ^c 106.0 (5) ^CrI 3 ^C 31 126.7 mm (3)

Comment:

and The number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b The atoms are labeled in accordance with Figure 1.

c Apostrophe marked atoms are symmetrical to the corresponding unlabeled atoms based on the symmetry -x, y, 1/2-z.

Table X

Coupling distances and angles of non-hydrogen atoms in the cation and crystallization solvent {NajgfCr (NC ^ H ^) ^ 2 (00 ^ Ηθ) ³

type ^b binding length, fw type ^b binding length ,, Na-Cl 2 q2 313 (3) ° 1 ' ^C 41 (jl 390) 1 44 ° ^C (jl 383 (7) At ... N | ' ^c 0.2 888 (4) At ... N ₃ ' ^c 0 2,830 (4) ^C 42 ^C 42 (jl 42 (1) ^C 42- ^C 43 Q1 42 ° 43 '° 44 qi 42

- 55 Table X - continued

type ^b and") angle, ε e ^ type ^b n angle, j & gj 0 ₁ NaN ₁ „ ^c 128.6 (3) ^C 41 ° ^C 44 107.9 (5) 0 ₁ NaN ₃ ' ^c 121.8 (3) N _r , NaN ₃ ' ^c 59,5 mm (3) ° ^C 41 ^C 42 109.0 (7) ^C 41 ^C 42 ^C 43 105.0 (8) ^{: JaO} 1 ° 41 125.7 (4) ^C 42 ^C 43 ^C 44 107.0 (7) ^At ° 1 ^C 44 121.8 (4) ° 1 ° ^C 44 ^° 43 ° ^C 107.6 (7)

Comment:

and the number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b The atoms are labeled in accordance with Fig. 2.

c The atoms marked with quotation marks are symmetrical to the corresponding unlabeled atoms based on the symmetry ψ-χ, 1/2 + y, 1/2-z.

4 '

Example VI

X-ray analysis of the relevant single crystal structure was identified [Cr (NC ^ H ^) ^ (OC ^ H ^)], shown in FIG. 5 ^X \ [Cr (NC ^ H ^) ^ (OC ^ H ^ KNa] ^. 4 (00 ^ Ηθ), fec, rpp <tr tr ρ 1 fp '* rp <

p r

56 of Product IV shown in FIG. 6.

The description of the single crystal sample and the method of its attachment during measurement are given below: color: red shape: rectangular parallelepiped dimensions: Q £ 50 x 0.55 x 0.63 mm crystal fixation: the crystal was glued into a thin-walled glass capillary and the capillary was sealed under nitrogen atmosphere of crystal orientation: the crystal was oriented with its longest edge almost parallel to the phi axis of the diffractometer of the width at half height based on a µm: 0.42 ° grid.

Spatial group and elementary cell data crystal group: monoclinic spatial group and number: 'P2 ₁ ~ C ₂ (No. 4) number of computer-centered reflections used to refine the elementary cell dimension by least squares: 15 20 20 ° ° C = 20 + 1 ° lattice constants a = y> 042 (2) Πΐη b = 1.7 242 (4) nm c = 3.3 025 (3) nm with estimated standard deviation:

V = ^ 162 (1) nrf α = 90.00 ° β = 106.54 (2) ° / = 90.00 °

Z = 2 = 9071073 molecular weight:

788.93 * kj · * <yy - Γ yy yy, f <yy yy yy yy-, yy yy yy yy,. · ..

- 57 calculated density: 1.212 g / cm ³ linear absorption coefficient: 0.32 am ~ K

Tables XI to XV summarize the resulting parameters for the molecular structure design shown in Figures 5 and 6.

Table XI

The atomic coordinates of non-hydrogen atoms crystalline [Cr (NC ₄ H _{4) 5} (OC ₄ H _s)] CNA] ₂ .4 (OC ₄ H _8), ^with type ⁵ fractional atomic coordinates * 10 ⁴ * 10 10 ⁴ y ⁴ equivalent of isotropic thermal parameter, B, hrvEx10

Anion

Cr 198 mm (1) 1477 2531 (2) 0,32 mm (1) ^K la 1694 (6) 2026 (2) 2028 (3) 0.40 (2) ^C la 1749 (6) 2782 (3) 1742 (5) 0.48 (2) ° 2a 2929 (7) 2926 (4) 1420 (6) Q66 (3) ° 3a 3661 (6) 2236 (4) 1554 (7) Q62 (2) ° 4a ' 2899 (7) 1695 (6) 1913 (4) 0,52 mm (2) ^K lb 1651 (6) 1087 (2) 3885 (3) 0 (40) ^C lb 1463 (7) 56O (&) 4575 (4) 0.48 (2) ^C 2b 2572 (8) 518 (5) 5423 (7) 0.82 (4) ^C 3b 3554 (7) 1064 (5) 5275 (5) 0.70 (3) ' ° 4b 2952 (7) 1382 (6) 4340 (4) 0.48 (2)

- 52 TABLE XI - Continued fractional type are equivalent isotroatomu 10 ^{b 4} x IO ⁴ 1 O y ^{te 4} from ^{the oven} to the parameters P ^el

B, nzv ^ xio ^c

^K lc -1326 (6) 1888 (2) 1250 (3) 0,38 mm (2) ^C lc -1200 (7) 2172 (3) 266 (5) q 51 (1) ^C 2o -2458 (7) 2270 (6) -476 (5) 0,58 mm (3) ^C 3 = -3435 (7) 2038 (7) 56 (7) 0,75 mm (3) ° 4c -2710 (6) 1826 (4) 1091 (5) 0/56 (2) ^N ia -32 (4) 2455/4) 3445 (4) 0.43 (2) ^c ia 504 (6) 2562 (4) 4505 (5) 0.49 (2) ^c 2a 107 (9) 3278 (6) 4774 (7) ¢ 72 (2) ° 3d -698 (7) 3629 (6) 3832 (5) ¢) 59 (2) ^c 4a -769 (6) 3108 (3) 3055 (7) 0,52 mm (2) ^K lě 315 (4) 505 (3) 1690 (3) 0.40 (2) ^c le -574 (7) 277 (6) 704 (5) 0.55 (3) ^C 2e -197 (9) -432 (6) 403 (6) 0 ^ 67 ^C 3e 990 (9) -662 (5) 1256 (7) (4) 79 (4) ^C 4e 1265 (7) -92 (3) 2016 (6) 0.51 (3) ° lf -1356 (3) 926 (2) 3083 (3) 043 ^C lf -2047 (6) 1244 (4) 3800 (5) 0.57 (3) ^C 2f -3263 (9) 713 (5) 3700 (8) 01/98 (4) ^c 3f -2833 (12) -21 (5) 3402 (7) 93, 93 mm (4) ° 4f -1903 (7) 17K5) kat ion 1 2724 (6) 0.64 (3) Ha, 2254 (2) 3336 (1) 3737 (2) 0.75 mm (1)

ρ ρ p. (( _{Γ Γ} · · ·>

Ρ r r

. Γ t. - * r

Ρ ρ

- 59 TABLE XI - Continued fractional type are equivalent isotroatomu ^b IO ⁴ x 10 ⁴ x ⁴ y 10 ^pLck thermal parameters

B, ^C cation BaCl 2

On ₂ 1430 (2) 974 (1) 126 mm (2) 0,62 mm (1) molecules crystallization solvent ° lg 4576 (5) 3329 (3) 4706 (6) 0.83 (2) % 5748 (8) 3100 (9) 4433 (8) 3,25 mm (6) ^C 2g 6723 (11) 2831 (12) 5281 (8) 3.56 (7) ° 3 _N 6503 (14) 3272 (12) 6146 (12) ^ 04 % 5037 (15) 3498 (12) 5737 (9) 1.70 (8) ° lh 2342 (6) 4602 (3) 3279 (5) 0.97 (3) ^C lh 1316 (12) 515K7) 2894 (9) 1 ^ 12 (4) ^C 2h 2017 (15) 5830 (8) 2541 (12) 3.53 (7) ^C 3h 3180 (11) 5561 (9) 2425 (9) 3.31 (6) % 3551 (12) 4848 (6) 3070 (12) 15 (5) ° li · 1391 (6) 1752 (3) -1377 (3) 0,80 mm (2) ^C li 2235 (20) 1594 (12) -1998 (12) 3.60 (8) ^C 2i 2716 (16) 2287 (15) -2337 (14) 3.65 (10) ^C 3i 1991 (27) 2906 (12) -1934 (15) 204 (11) ^C 4i 1010 (15) 2533 (6) -1523 (8) 3 ^ 28 ° 13 3037 (6) 155 (3) -264 (4) 0,72 mm (2) ^c iá 4389 (9) 48 (7) 427 (8) 1,13 mm (5)

e * y r 'f y r y r y

- € 0 Table XI - continued atom type ^b fractional coordinates 10 ⁴ x loS 10 ⁴ z equivalent isotropic thermal parameters:

M, M ² x 10 ^c

2j 4998 (15) -571 (9) -23 (15) 1/74 (7) 3j 4001 (12) -840 (7) -1006 (9) 1.27 (6) 4j 2728 (12) -493 (6) -974 (7) 92, 92 mm (4)

and Numbers in brackets represent chilled: standard deviations of the last significant digit.

b The atoms are indicated in accordance with Figures 1 and 2.

c This is one third of the foot of the orthogonal tensor Bij.

re r, rr rrr 'recr rrrrtrrr ^r t <crrr rerr reerre _r . _»R r .- rrretr <r ··" rrr r ·. · R "- - <>

- 61 T a b u 1 k.a XII

Anisotropic thermal parameters of non-hydrogen atoms in crystalline [Cr (Ν0 ₄ Η ₄ > ₅ (Ού ^ Ηθ)] [Na] ₂ ^{a> b}

atom type ⁰ Anisotropic thermal ^B 33 parameter ^B 12 ^B 13 ^B 23 ^B U ^B 22 Anion Cr 0.29 mm (1) 0,31 mm (1) 0,38 mm (1) 0.01 mm (1) 12) 12 (2) 0.01 mm (1) ^N la 0,33 mm (2) 0.44 (3) 0.44 (3) -q0l (1) 0.11 (2) 05) 05 (1) ^C la 0.48 (4) 0,37 mm (3) 0.59 (4) '0.0 0 (2) 0,15 mm (3) 03) 03 (2) ^C 2a 0.55 (4) 0.61 (5) 0.90 (5) -0.19 (4) 0.34 (4) 013 (3) ^C 3a 0,37 mm (3) 0.82 (6) 0.76 (5) -009 (2) 0,33 mm (3) 0,02 mm (4) ^C 4a 0.40 (3) 0.64 (5) 0.52 (4) ¢ 04 (2) 0,16 mm (3) 0.05 (3) ^N lb 0,36 mm (2) 0.44 (3) 0,36 mm (3) 07) 07 (1) 05, 05 (1) 0.12 mm (2) ^C lb 0.52 (4) .0.51 (4) 0.40 (3) -0.01 (3) 09) 09 (2) 0,10 mm (3) ^C 2b 0.73 (5) 0.85 (6) ' 0.83 (6) 0,02 mm (5) 0,13 mm (4) 0.44 (5) ^C 3b 0.51 (4) 0.88 (6) 0.54 (4) 0,00 (3) - 0,13 mm (3) 0,12 mm (4) ° 4b 0.41 (3) 0.55 (4) 0,45 mm (3) 00) 00 ¢ 05 (1) 0 _f 04 (3) ^N lo 0,33 mm (2) £} 4X <3) 0,39 mm (3) 0,04 mm (2) ¢¢ 9 mm (2) £) 0) 1 (1) ^C lo 0.52 (4) 0.51 (4) 0.51 (4) ¢ 06 (2) ¢ 16 mm (3) 0.05 (3) ^C 2o 0.64 (5) 0.62 (5) ¢ 37 mm (4) - () /) 1 (4) ' - ^ 4 0,04 mm (4) ^C 3c 0,32 mm (3) 092 (7) 0.89 (6) . ¢ 04 (4) ' - <? «3 £ (29) ^C 4c 0,42 mm (3) 0.78 (5) ¢) 48 (3) -001 (2) 009 (2) £ (14) ^K ia 031 (1) 0.44 (3) q56 (2) 0,04 mm (2) 0.13 (2) ’ -0.01 (3) ° ia 0.44 (3) 0.60 (5) 0.39 (4) “0.05 (3) ¢ 08 (2) -0.11 (31

E Γ r e

Table XII - Continuation type Anisotropic thermal parameter (74 ² χ1θ) atom ^{0 B} 11 ^B 22 ^B 33 ^B 12 . ^B 23 Zq ^B 23 ^C 2d 0.63 (4) 0.70 (6) 0.84 (6) - (^ 11 (4)) () 20 (4) '0.47 (5) ^C 3d 0.69 (4) 0.43 (4) 0.73 (5) 0.09 (3) 0.32 (4) -0.14 (4) ^C 4d 0,42 mm (3) 0.53 (4) 0.63 (4) 0.08 (3) 0.17 (3) 03, 03 (4) ^N le 0.47 (3) 0,36 mm (3) 0.39 (3) -0.03 (2) 0.17 (2) - (j07 (2)) ^C le 0.59 (4) 0.49 (4) 0.53 (4) -101 (3) 0.11 (3) - (01) (4) ^C 2e 0 92 (4) 0.48 (4) 0.69 (5) -020 (1) 0.36 (4) - (26) (4) ° 3e 0.91 (6) 0.45 (5) 0.04 (4) 0.37 (5) '0.13 (5) ° 4θ 0.62 (4) 0.23 mm (3) 0.69 (5) () 07 (3) 0.20 (4) -0.0-7 (3) 0.40 (2) 0.42 (2) 0.55 (2) -0.04 (2) ¢) 20 (2) 0.02 (2) ^C lf 0.61 (4) 0.64 (5) 0.60 (4) -0.02 (3) 0.39 (3) 004 (3) ^C 2f 0.81 (6) 0.95 (7) 3.44 (8) -02 (5) 0.74 (6) 0.01 (6) ^C 3f 3.09 (7) 0.80 (6) -0 (7) -07 (5) 0.75 (6) -0 _f 03 (6) ^C 4f 0.61 (4) 053 (3) ^ 85 (5) '0.27 (4) 030 (4) -0.16 (4) ι 1

cation 1

^Ka l 0.57 (2) 0.71 (2) 0.95 (2) - ^, 13 (1) 21) 21 (2) -002 (1) <· ' cation 2 On ₂ 0,68 mm (2) ¢ 69 mm (2) 056 (2) '0.02 (1) 0.30 (1) -0.03 (2) solvent crystallization molecules ° lg 0,58 mm (3) ¢, 95 mm (4) 092 (4) -0.03 (3) 1.08 (8) 00 (7) 0.15 (3) ^ 2 (4) ^c ig 0.54 (5) H (14) 0.29 (5) - (9.07 (9))

«♦ Γ

C Γ Γ _Γ . · Γ · r

- 63 Table XII - continued

atom type ⁰ Anisotropic thermal] parameter ^B 12 - · (nrtčx10) ^B I3 ^B 23 ^B 11 ^B 22 ^B 23 ^C 2g 0.96 (7) ^ 26 (14) 321 (8) 0.52 (9) C> 43 (7) φι (ιο) ° 3 _N 1.29 (10) 377 (20) 348 (12) 0.52 (12) -0.56 (9) -334 (12) ^C 4g 1.34 (10) 350 (17) 328 (9) 044 (12) 0.39 (91 -089) ° lh 0.71 (4) ¢ 68 (3) 352 (5) -0.08 (3) 0.32 (4) -003 (3) ^C lh 0.92 (7) 095 (7) 1.44 (9) -0.02 (6) 0.28 (7) -0.03 (7) ^C 2h 2 * 12 (15) 308 (9) 340 (9) ¢ 36 (9) 050 (10) 0.66 (8) ^C 3h 0.99 (8) 375 (13) 301 (7) -0.06 (9) -0.02 (6) 0.32 (9) ^C 4h 0.99 (8) 0.79 (7) 368 (12) -0.13 (6) 0.38 (8) 0.29 (8) ° li 0.98 (4) 0.82 (4) 0,73 mm (3) ¢ 08 (2) 0.47 (3) ¢ 13 (3) ^ 30 (15) 368 (11) 0,08 mm (11) yi (12) 0.74 (10) ^C 2i 312 (9) 322 (22) 356 (14) 0/1 (11) ¢ 28 (11) ¢ 23 (16) ° 3i 370 (27) 324 (11) 135 (11) -0.93 (15) ^ 99 (15) 0.34 (10) ° 4i 323 (12) 0.81 (7) 306 (7) 0/2 (8) ¢ 90 (9) 03K6) ° lj ¢ 59 mm (3) 0.64 (3) 0.94 (4) 0.05 (3) 0.22 (3) -0.21 (3) 0.88 (7) 3OK8) 333 (8) 0.19 (6) ¢ 02 (6) -0.58 (6) 0.94 (8) 390 (15) 2 * 05 (12) ¢ 73 (10) -0.11 (9) -0.90 (13) ^C 3 ₅ 0,83 mm (7) i330 (9) 360 (9) ¢ 16 mm (7) ¢ 20 (7) -0.86 (9) % ¢), 82 (7) 304 (7) 0.92 (7) -0.07 (6) ¢ 29 (5) - (41) (6)

and The number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b Anisotropic thermal parameter form ,,;

c The atoms are labeled in accordance with Fig. 1 ^ 2-,

- 64 Table XIII

Atomic coordinates of hydrogen atoms in crystalline CCr (NC ₄ H ₄ ) ₅ (OC ₄ H ₈ )] [Na] ₂ ,

atom type ^b fractional LO x ⁴ coordinates 10 ⁴ y 10 ⁴ z ^H la 1061 3165 1756 ^H 2a 3182 3406 1151 ^H 3a 4547 2153 1428 ^H 4a 3162 1162 2059 ^H lb 637 254 4479 ^H 2b 2692 174 6022 ^H 3b 4453 1179 5753 ^H 4b 3373 1775 4016 ^H lo -326 2281 132 »2c -2637 2453 -1199 ^H 3o -4426 . 2031 -243 ^H 4c -3137 1655 1623 ^H ia 1070, 2197 4997 ^H 2d ' 349 3499 5480 ^H 3d -1115 4135 3762 ^H 4d -1278 3184 2317 ^H la -1346 578 293 ^H 2e -630 -712 -243 ^H 3e 1503 -1135 1285

- 65Table XIII - continued atom type ^ fractional coordinates

10 ⁴ x 10 ⁴ y 10 ⁴ X

«4a 1999 -107 2676 " «Ifa -1447 1250 4520 ^H lfb -2359 1762 3588 »2fa -4069 899 3170 ^H 2fb -3468 674 4380 ^H 3fa -2341 -312 4022 ^H 3fb -3620 -314 2996 ^B 4fa -2417 184 1980 ^H 4fb -1165 -201 2831

crystallization solvent

«Lga 6103 3536 4135 «Igb 5503 2694 3909 «2ga 6629 2283 5371 «2gb 7629 2940 5209 ^H 3ga 6644 2947 6766 ^H 3gb 7102 3717 6322 «4ga 4960 4045 5839 «4gb 4493 3223 6118 «Lha 596 4950 2301 «Lhb 921 5310 3451 «2h ^x ,. 2205 6231 3073 «2hb 1449 6034 1874 «3ha 3066 5447 1684

- 66 Table XIII - continued

atom type * ¹ Fractional 10 ⁴ x coordinates 10 ⁴ y 10 ⁴ z ^H 3hb 3908 5936 2669 ^H 4ha 4260 4953 3725 ^H 4hb 3874 4459 2671 «Lia 3007 1289 -1594 «Lib 1721 1306 -2615 «2ia 3703 2328 -2031 ^H 2ib 2496 2303 -3103 «3ia 1541 3249 -2509 ^H 3ib 2638 3195 -1381 «4ia 101 2580 -2020 ^H 4ib 1010 2761 -851 ^H lja 4929 513 470 ^H ljb 4341 -91 1129 «2 _á á 5823 -388 -178 «2ib 5232 .-992 479 «33 a 3930 -1396 -1018 ^H 3jb 4261 « -668 -1623 «4 ₃ a 2185 -862 -715 «43b 2215 -324 -1678

- 67 Notes:

and hydrogen atoms were included in the calculation of the structural factor as idealized atoms (assuming sp or sp ^ hybridization of carbon atoms and C-H bond length)

0.096 nm running on the corresponding carbon atoms. The isotropic thermal parameter of each hydrogen atom was determined to be 1.2 times the equivalent isotropic thermal parameter of the carbon atom to which the hydrogen atom is covalently bonded.

b Hydrogen atoms are designated with the same numerical and equal subscripts as the carbon atoms to which they are bound. If necessary, an additional subscript a or b is used to distinguish between hydrogen atoms bound to the same carbon atom.

c r * · e r f r

- 68 Table XIV

Bonding distances of non-hydrogen atoms in crystalline [Cr <NC ₄ H ₄ ) ₅ (OC ₄ H ₈ )] [Na] ₂ . 4 (00 _{4 θ} )

type ^b binding length, iV. type ^b binding length Cr-N _la 0.2 035 (6) ^Na i- ° i _g 0.2 314 (6) Cr-K _lb 0.2 056 (5) ^At 1 ° -h 0.2 271 (8) Cr-N _1c 0,2 044.C5) Or- _ld 0.2 114 (6) ^Ka 2- ° 11 0.2 365 (7) Cr-K _le 0.2 024 (6) ^Ka 2 ”° lj 0.3 307 (7) ^Cr -1f 0.2 120 (5) ^C 1 ^{-C 2} g 0.1 33 (2) ° 2g ^C 3g ' qi 43 ^{E C} IA-Ia 0.1 36 (1) ^C 3g- ^C 4g 0 _f l 48 (2) ^H 1a- ^C 4a 0.1 38 (1) ^C 1h ” ^C 2h 0.1 51 (2) ^N 1b ~ ^C 1b 0.1 33 (1) ^C 2h ^C 3h 0.1 30 (2) ^N 1b - ^C 4b 01 37 ^C 3n ' ^C 4h 0.1 48 (2) ^N 1c- ^C 1c 0.1 41 mm (1) ^{C 1 C} 2i 0.1-41 (3) ^N 1c-4c 0.1 35 (1) ^C 2i ' ^C 3i 0.1 47 (3) ^N ld ^C ld 0.1 34 (1) ^C Si ' ^C 4i 0.1 40 (3) ^N 1fl ^C 4d QX 36 ^c ia ^_0 2á 0.1 44 (2) ^N le- ^C le 0.1 40 (1) ^C 23 ' ^C 33 0.1 46 (2) ^N le ' ^C 4e 0.1 39 (1) ^C 3d- 43 0.1 42 (2)

C ř>

- 65 Table XIV - continued

type ^b binding length, hM. type ^b bond length, ti ° lf- ^C lf 0.1 42 (1) ° lg ‘° lg 0.1 38 (1) ° lf “ ^C 4f 0.1 44 (1) ° lg '° 4g 0.1 32 (1) ° lh ^C lh 0.1 38 (1) ° 1 _and - ° 2a 6,1 39 (1) ° lh ^C 4h 0,1,39 mm (2) ° 2a - ° 3a 0.1. 38 (1) ° li? .Li 0.1-36 (2) ^C 3a- ^C 4a 0.1 37 (1) ° ^C 4i 0.1; 40 mm (1) ° 1b- ° 2b 0.1 33 (1) ° lj ^C lj 0.1.41 (1) ^C 2b- ^C 3b 0.1 42 (1) ° i3 ° 4d 01 43 ^C 3b ” ^C 4b 0.1 31 (1) ^C 1c ^C 2c 0.1 37 (1) ^{Na- C} 1a 0.2 678 (8) ^C 2c- ^C 3c 0.1 41 mm (1) ^Na i- ^N ia 0.2 688 (7) ^C 3c ' ^C 4c 0.1 39 (1) ^Ka 1 ° ld 0.2 621 (9) ^C 1d ” ^C 2d 0.1 37 (1) ^C 2d ^E 3d 0.1 40 (1) * ^C 3d ' ^C 4d 0.1 34 (1) ^Ka 2 ° 4a f, 2,681 (7) ^C le ' ^C 2e 0.137 (1) ^At 2 “ ^C Ie 0.2 630 (9) ^c 2e- ₃ e 0.1 43 mm (1) ^C 3.- 4e P, 1 37 ^C 1f " ^C 2f 0.1 50 (1) ^C 2f ^C 3f 0.1 43 (2) ° 3f- ^c 4f 0.149 (2.) ...... - .. ............... -......  - · -............. and the number in parentheses represents the estimated authoritative

numeral deviation at last valid digit · b Atoms are marked in accordance with figure! ▼ ·

Table XV

Coupling angles of non-hydrogen atoms in crystalline C Cr (NC ₄ H ₄ ) ₅ (OC ₄ H ₈ )] [Na] ₂ .4 (OC 4)

^N la ^CrN 1b

91.2 (2) ° lg ^To 1 ° lh 92.3 (3)

^K la ^CrN lc 91,4 mm (2) ° lg ^Na l ^C la 114.3 mm (3) «La ^ ld 91.1 (2) ° lg ^to Ad 139.6 (3) ^K la ^Ork le 92.8 mm (2) ° ig ^Na i ^c ia 118.0 (3) ^N la ^CrO 1f 178.7 (2) ° lh ^Na l ^C la 95,6 mm (3) ^N lb ^Cr \ 176.2 mm (2) ° ih ^Ka i ^K i 127.0 (2) ^N ib ^arN ia 86.7 (2) ° lh ^Na l ^C ld 132.1 mm (3) ^N 1b ^Cr 93.3 mm (2) ^C la ^Na Ad 75.1 mm (2) ^K 1b ^CrO 1f 88,5 mm (2) ^C la ^Na l ^C ld 103.1 (3) ^N ic ^OrN ia 90,4 mm (2) ^N ld? ^{and C} l ld 29,3 mm (2) ^K lc ^CrK le 89,4 mm (2) ^The LC LF ^CR c 88.8 (2) A ° li ^Na 2 ° lj 90.7 mm (3) ^K i ^CrN le 176.1 mm (2) ° li ^Ka 2 ^C 4a 109.3 mm (3) ^K i ^CrO if 87,6 mm (2) ° li ^Na 2 ^C le 131,5 mm (2) ^K le ^CrO 1f 88,5 mm (2) X ° lj ^Na 2 ^C 4a 103.2 mm (2) ° lj ^Na 2 ^C le 115.1 (3)

- 71 Table XV - continued

type ^b (. *) angle, (degj type ^b F) angle, .ie ^OrN la ° la 128.7 (5) ^C 4a ^Na 2 ^C le 103,9 mm (3) ^0rN and ^C 4a 126.3 (5) ^CrN 1b ^C 1b 127.0 (4) ^Na 1 ° lg ° lg 131,4 mm (6) ^CrN 1b ^C 4b 127.3 (5) ^Na 1 ° lg ^G 4g 124.0 (8) ^Crli lo ° lo 128.5 (5) ^ ^and 1 ^G 1h ^G 1h 132,2 mm (7) ^{Ork Lc} 4 = 126.7 (5) ^At 1 ° lh ^C 4h 116.6 (6) ^CrN ia ° id . 127.7 (5) ^To 2 ° li ^C li 120.9 (8) ^Cril ld ^C 4d 125.7 (5) ^At 2 ° ^C 4i 126.8 (7) ^CrN le ^C le. 127.7 (5) ^Ca 2 ° lj ^C lj 123.1 (6) ^Crl le ° 4e 126,2 mm (4) ^Ca 2 ° ^C 43 125.8 (5) Cr ° _lf ° _lf 126,4 mm (4) ^C 1g ° 1g ^C 4g 104.3 (8) ^CrO 1 ^C 4f 123.1 (5) ^C 1h ° 1h ^C 4h 108.9 (9) ^{C 1} ° ^C 4i i 107.8 (11) ° la ^K la ^C 4a 105.0 (6) ^C 13 ° lj 43 ° 107.7 (7) ° la ^K lb ^C 4b 105.2 (5) ° 1c ^N 1c ^C 4e 104.0 (5) ° lg ^C 1g ^C 2g 111 mm (1) ^C ld ^N ld ^G 4d 106.6 (6) ^G 1g ^H 2g ^G 3g 103 mm (1) ^C le ^N le ^C 4e 106.0 (6) ^C 2g ^C 3g ^C 4g 103 mm (1) ^C 3g ^C 4g ° lg 110 (IX

- 12 Table XV - continued Type ¹ Type ^{1 C} lf ° lf ^C 4f

110.5 (6) ° ^C H ^C H ^C H ^C 2h 2h 3h ^C

106 mm (1)

106 mm (1)

^N la ^C la ^C 2a 111.1 (7) ^C 2h ^C 3h ^C 4h 109 mm (1) ^C 1a ^C 2a ^C 3a 106.1 (8) ^C 3h ^C 4h ° lh 106 mm (1) ^C 2a ^C 3a ^C 4a 107.5 (7) ° li ^C li ^C 2i 110 mm (2) ^C 3a ^C 4a ^N 1a 110.3 (7) ^{C 1 C} 2i ^C 3i 105 mm (2) ^N 1b ^C 1b ^C 2b 110.6 (7) ^C 2i ^C 3i ^C 4i 106 (23 ^C 1b ^C 2b ^C 3b 107.6 (8) ^C 3i ^C 4i ° li 107 mm (1) ^C 2b ^C 3b ^C 4b 104.4 (7) ° lj ^C lj ^C 2j 106 mm (1) ^C 3b ^C 4b ^N 1b 112,2 mm (7) ^C 1h ^C 2j ^C 3j 109 mm (1) ^K 1c ^C 1c ^C 2c 112,4 mm (7) ^C 2j ^C 3j ^C 4j 104 mm (1) ^C 1c ^C 2c ^C 3c 104.5 (7) ^C 3j ^C 4j ° lj 108 mm (1) ^C 2c ^C 3c ^C 4c 107.8 (7) ^C 3c ^C 4c ^N lc 111,2 mm (7) ^Na l ^C la ^N la 95.0 (4) ^N 1d ^C 1d ^C 2d 109.0 (7) ^Na 1 ^C and ^C 2a 106.7) 5) Ld ^{C C C} 2d 3d 107.6 (8) ^Na l ^N ld ^Cr 107.7 (3) ^C 2d ^C 3d ° 4d 105.4 (8) X ^Na l ^N ld ^C ld 72.6 (4) ^C 3d ^C 4d ^N ld 111.5 (7) ^Na 1 ^N ld ^C 4d 86.4 (4) ^N le ^C le ^C 2e 111.0 (7) ^Na l ^C ld ^N ld 78.1 mm (4)

- 13 Table XV - continued

type ^b l ·) angle, type ^b angle, ^C le ^C 2e ^C 3e 105.2 (7) ^Ka l ^C ld ^C 2d 85.1 mm (6) ° ° 2e 3e 4e ⁰ 108.4 (81 ° 3e ° 4e ^K le 109.5 (7) ^Ka 2 ^C 4a ^N la 90,2 mm (3) ^Ka 2 ^C 4a ^C 3a 104.0 (5) ° 1f ^C 1f ^C 2f 104.4 (7) ^At 2 ^C le ^K le 78.1 mm (4) ^C 1f ^C 2f ^C 3f 105.0 (9) ^Na 2 ^C le ^C 2e 91.7 (6) ^C 2f ^C 3f ^C 4f 104.9 (9) ^C 3f ^C 4f ° 1f 104.7 (7)

Comment:

and the number in parentheses represents the estimated standard deviation of the numeral at the last valid digit.

b Atoms are labeled in accordance with Figure 1.

74. Example VII

The reaction product obtained by the reaction of 2,5-dimethylpyrrolidide and chromium (II) chloride (light blue solid, product VI) was used to prepare the active catalyst. This product was prepared as follows: 2,5-dimethylpyrrole (5.0 mL / 49.1 mmol) was mixed with an excess of sodium (40% dispersion in white spirit) in tetrahydrofuran (125 mL) at ambient temperature. The mixture was refluxed under a nitrogen atmosphere for 12 hours and then filtered to remove excess sodium. The 2,5-dimethylpyrrolidone was not isolated and was mixed directly with the chromium chloride (3.03 g / 24.7 mmol) at ambient temperature directly in situ. The reaction mixture was refluxed under nitrogen for 48 hours. Filter the gray-green solution through a medium porosity frit at ambient temperature. The solvent is stripped off in vacuo and the residue is removed by vacuum drying for 12 hours. The obtained gray-green solid was washed with pentane to give a pale blue solid, product VI, which was filtered off. The product VI is used in the preparation of the active catalyst without purification.

Example VIII

Preparation of catalysts

All polymerization experiments were carried out in a 2 liter reactor by slurry polymerization. Isobutane and temperature are used as solvents

- 15 in the reactor is 90 ° C. The overpressure in the reactor was maintained at 50 psi and ethylene was charged as needed.

The reactor is charged as follows: The reactor is purged with a nitrogen stream at 100 ° C for at least 15 minutes. Thereafter, the temperature in the reactor is lowered to 90 ° C and a pre-weighed amount of supported chrompyrrolidide catalyst is introduced under a slight countercurrent of nitrogen. Thereafter, 1 liter of isobutane is introduced into the reactor and finally ethylene is introduced into the reactor up to the desired pressure.

The ethylene consumption is measured using a pre-calibrated flow meter. After every 30 minutes of the experiment, samples of the liquid reaction mixture are sampled without releasing the pressure in the reactor. Sampling is carried out by means of a steel sample cylinder, which is adapted to the shape of the reactor and comprises a frit-tipped tube extending down to the bottom of the reaction vessel. The filling of the cylinder is carried out up to an overpressure of 1.37 to 2.06 MPa. Samples taken in this way are analyzed by gas chromatography and gas chromatography combined mass spectrometry. Selectivity was normalized to 100%. Upon completion of the experiment, the reactor is vented to atmosphere and the solid is separated from the liquid by decantation. The solid is dried at 100 ° C in a vacuum oven and weighed. The solid product yield is determined by weighing the solid associated with the catalyst residues and subtracting the original catalyst weight from this value.

The yield of the volatile product is determined by subtracting the solid product yield from the total amount of ethylene consumed detected by the flow meter.

As shown in Table XVI, a typical activity value in the range of 300 to 1500 g of product per gram of catalyst per hour is typical for a 30 minute experiment. The product obtained generally contains 97 to 99.5% by weight of liquid and 0.5 to 3% by weight of waxy polymer. The liquid fraction has the following typical composition: 85% hexene, 11% decene and 2% tetradecene, based on the total weight of the liquid fraction. The remainder of the liquid product is traces of different olefins, which generally comprise a total of 1 to 2% by weight of the product mixture (see Table XVII).

Active catalysts are prepared from chrompyrrolidide complexes as follows. For each alarm with toluene and / or pentane, 15-30 ml of liquid is used.

Attempts λ

0.158 g of product V (prepared in THF solvent), which was heated for 4 hours under a stream of nitrogen to remove residual THF, was suspended in 15 ml of toluene at ambient temperature. To the solution was added 9.0 mL of a 1 L solution of triethyl aluminum (TEA) in hexane solution

77 and the mixture was stirred for 24 hours. Immediately after the addition of TEA, a brown solution formed and the product V completely dissolved. To the solution was added aluminophosphate (AlPO 4, p / Al molar ratio 0.4) (2.00 g) and the solution was stirred for an additional 24 hours. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. 0.3143 g of this catalyst was charged directly to the polymerization reactor. After the catalyst has been introduced but before the isobutane (reaction solvent) is introduced, 1.0 ml of a 0.5% solution of triethyl aluminum (TEA) in heptanes is introduced into the reactor to remove the poisons contained in the feed.

Experiment 2

0.081 g of product V (prepared in tetrahydrofuran as solvent) was heated under heating. 4 hours under a stream of nitrogen to remove traces of tetrahydrofuran are suspended in 15 ml of diethylene-zene at ambient temperature. To the solution was added 2.00 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 24 hours. Immediately after the addition of TEA, a brown solution formed and the product V completely dissolved. To the solution was added aluminophosphate (AlPO 4, molar ratio P (Al = 0.4) (1.50 g) and the mixture was stirred for an additional hour. The supported catalyst as a brown solid was filtered from the solution, washed twice

73 dimethylbenzene and then twice with pentane. 0.4333 g of this catalyst was charged directly to the polymerization reactor. After the catalyst was introduced but before the isobutane (reaction solvent) was introduced, 3.0 ml of a 0.5% triethyl aluminum (TEA) solution in heptanes was introduced into the reactor to remove the poisons contained in the feed.

Experiment 3

0.093 g of product V (prepared in dimethoxyethane as solvent) is suspended in 15 ml of toluene at ambient temperature. To the solution was added 5.00 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 24 hours. Immediately after the addition of TEA, a brown solution formed and the product V completely dissolved. Aluminophosphate (AlPO 4, P / Al molar ratio = 0.4) (1.00 g) was added to the solution and the mixture was stirred for an additional 24 hours. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. 0.1564 g of this i

The catalyst is charged directly to the polymerization reactor. After the catalyst was introduced but before the isobutane (reaction solvent) was introduced, 3.0 ml of a 0.5% solution of triethyl aluminum (TEA) in heptanes was introduced into the reactor to remove the poisons contained in the feed. _x

Experiment 4

0.080 g of product I (prepared in tetrahydrofuran as solvent) is suspended in 15 ml of toluene at ambient temperature. To the solution was added 6.00 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 16 hours. Immediately after the addition of TEA, a brown solution formed and product I completely dissolved. Eiluminophosphate (AlPO 4, P / Al molar ratio = 0.4) (1.50 g) was added to the solution, and the mixture was stirred for an additional 16 hours. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. 1.1988 g of this catalyst were charged directly to the polymerization reactor.

Experiment 5

0.079 g of product II (prepared in tetrahydrofuran as solvent) is suspended in 15 ml of toluene at ambient temperature. To the solution was added 2.00 ml of a 1M solution of triethylaluminum (TEA) in toluene, and the mixture was stirred for 8 hours. Immediately after the addition of TEA, a brown solution formed and product II completely dissolved. Aluminophosphate (AlPO 4, P / Al molar ratio = 0.4) (0.50 µg) was added to the solution, and the mixture was stirred for an additional 16 hours. The supported catalyst catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. 0.4829 g of this catalyst was charged directly to the polymerization reactor.

P o k u s 6

0.071 g of product V (prepared in tetrahydrofuran as solvent), which was heated for 4 hours under a stream of nitrogen to remove traces of tetrahydrofuran, was suspended in 15 ml of toluene at ambient temperature. To the solution was added 2.00 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 1 hour. Immediately after the addition of TEA, a brown solution formed and the product V completely dissolved. Silica (2.52 g) was added to the solution, and the mixture was stirred for another two minutes. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. All the catalyst is charged directly to the polymerization reactor.

Attempt 7

0.103 g of product II (prepared in tetrahydrofuran as solvent) is suspended in ml of toluene at room temperature. To the solution was added 1.00 mL

Of a 1.9 M solution of triethyl aluminum (TEA) in toluene and the mixture was stirred for 10 minutes. Immediately after the addition of TEA, a brown solution formed and product II completely dissolved. To the solution was added alumina (2.27 g) and the mixture was stirred for another two minutes. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. 1.2926 g of this catalyst were charged directly to the polymerization reactor.

Attempt 8

0.120 g of product I (prepared in tetrahydrofuran as solvent) is suspended in 15 ml of toluene at ambient temperature. To the solution was added 2.00 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for two days. Immediately after the addition of TEA, a brown solution formed and product I completely dissolved. Silica (1.00 g) was added to the solution, and the mixture was stirred for another three weeks. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. All the catalyst is charged directly to the polymerization reactor.

- 82 Attempt 9

0.106 * 5 of product III (prepared in tetrahydrofuran as solvent) is suspended in 15 ml of toluene at ambient temperature. To the solution was added 2.50 mL of a 1.9 M solution of triethyl aluminum (TEA) in toluene, and the mixture was stirred for two hours. Immediately after the addition of TEA, a brown solution formed and product III completely dissolved. To the solution was added aluminophosphate (AlPO4, P / Al molar ratio = 0.4) (0.65 g) and the mixture was stirred for another two hours. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. All of this catalyst is charged directly to the polymerization reactor. After the catalyst was introduced but before the isobutane (reaction solvent) was introduced, 1.5 ml of a 10% solution of triethyl aluminum (TEA) in pentane was introduced into the reactor to remove the poisons contained in the feed.

Attempt 10

0.030 g of product V (prepared in tetrahydrofuran as solvent), which was heated at 80 ° ^C for 4 hours under a stream of nitrogen to remove traces of tetrahydrofuran, was suspended in 15 ml of toluene at ambient temperature. To the solution was added 3.00 ml of a 1M tri-solution.

- 83 ethyl aluminum (TEA) in hexanes and stirred for 16 hours. Immediately after the addition of TEA, a brown solution flows and the product V completely dissolves. Aluminophosphate (AlPO 4, P / Al molar ratio 0.9) (2.0 g) was added to the solution, and the mixture was stirred for an additional 16 hours. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. 0.322 g of this catalyst is charged directly to the polymerization reactor.

Attempt 11

0.067 g of product V (prepared in tetrahydrofuran as solvent) is suspended in 15 ml of pentane at ambient temperature. To the solution was added 4.00 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 24 hours. Immediately after the addition of TEA, a brown solution formed and the product V completely dissolved. Aluminophosphate (AlPO 4, P / Al -0.4 molar ratio) (1.00 g) was added to the solution, and the mixture was stirred for an additional 24 hours. The supported catalyst as a brown solid was filtered from the solution and washed twice with pentane. All of this catalyst is charged directly to the polymerization reactor. After the catalyst was introduced but before the isobutane (reaction solvent) was introduced, 3.0 ml of a 0.5% triethyl aluminum (TEA) solution in hepts was introduced into the reactor to remove the poisons contained in the feed.

- 84 Experiment 12

0.073 g of product V (prepared in tetrahydrofuran as solvent), which was heated for 4 hours under a stream of nitrogen to remove traces of tetrahydrofuran, was suspended in 15 ml of toluene at ambient temperature. To the solution was added 6.0 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 24 hours. Immediately after the addition of TEA, a brown solution formed and the product V completely dissolved. Phosphated silica (P / SiO ₂ ) (7.00 g) was added to the solution and the mixture was stirred for an additional 24 hours, during which time it almost became decolorized. The supported catalyst as a brown solid was filtered from the solution and washed twice with toluene and then twice with pentane. 2.85 g of this catalyst were charged directly to the polymerization reactor.

Attempt 13

0.125 g of product II is suspended in 15 ml of diethylbenzene at ambient temperature. To the solution is added 9.0 ml of a 1M solution of triethyl aluminum (TEA) in hexanes and the mixture is stirred for 8 hours. Immediately after the addition of TEA, a brown solution was formed and the product II dissolved effectively. To the solution was added fluorinated alumina (E / AlgO 4) (2.00 g) and the mixture was stirred for an additional 12 hours. The supported catalyst as a brown solid was filtered from the solution and washed twice

Toluene and then twice with pentane. 0.5477 g of this catalyst was charged directly to the polymerization reactor.

Attempt 14

0.125 g of product VI is suspended in 15 ml of toluene at ambient temperature. To the solution was added 1.5 mL of a 1M solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 10 minutes. Immediately after the addition of TEA, a reddish-brown solution was formed and the product VI completely dissolved. Silica (S10g) (2.00 g) was added to the solution, and the mixture was stirred for an additional 1 minute, during which time it almost became decolorized. The supported silica catalyst as a reddish brown solid was filtered from the solution and washed twice with toluene and then twice with pentane. All of this catalyst is charged directly to the polymerization reactor.

Attempt 15

0.30 g of product V (prepared in dimethoxyethane as solvent) was dissolved in 15 ml of dimethoxyethane (DME) to give a green solution. The solution was treated with aluminophosphate (0.6 g, AlPO4, P / Al molar ratio = 0.4) (2.00 g) and the mixture was stirred _x for 1 hour. The green supported substance is filtered from the solution, washed

86 with dimethoxyethane and dried in a stream of nitrogen at 90 ° C. This material was then stirred with 15 ml of toluene and 3 ml of triethylaluminum (Aldrich, 1.0M, hexanes) for a further 3 hours. The supported catalyst as a brown solid was filtered off and washed with pentane and dried in vacuo. 0.4609 g of this catalyst was charged directly to the polymerization reactor. After the catalyst was introduced but before the isobutane (reaction solvent) was introduced, 3.0 ml of a 0.5% triethyl aluminum (TEA) solution in heptanes was introduced into the reactor to remove the poisons contained in the feed.

Attempt 16

0.05 g of product V (prepared in tetrahydrofuran as solvent), which was heated for 4 hours under a stream of nitrogen to remove traces of tetrahydrofuran, was suspended in 15 ml of benzene at ambient temperature. To the solution was added 4.0 mL of a 1L solution of triethyl aluminum (TEA) in hexanes, and the mixture was stirred for 2 hours. Immediately after the addition of TEA, a brown solution formed and the product V completely dissolved. Aluminophosphate (AlPO4, P / Al molar ratio = 0.4) (1.00 g) was added to the solution and the mixture was stirred for an additional hour. The supported catalyst as a brown solid is filtered from the solution and washed twice with benzene and then twice with pentane. All of this catalyst is charged directly to the polymerization reactor. After putting

87 catalyst, but before the isobutane (reaction solvent) is introduced, 3.0 ml of a 0.5% triethyl aluminum (TEA) solution in heptanes is introduced into the reactor to remove the poisons contained in the feed.

Will he try?

0.1610 g of product I is introduced directly into the reactor at 90 ° C. The reactor is charged with 1 liter of isobutane and then ethylene is introduced up to a pressure of 100 psi. No ethylene consumption was detected. Therefore, hydrogen gas up to 50 psi is introduced into the reactor, but ethylene is not consumed. Ethylene is consumed only after adding 2.0 ml of a 1M solution of TEA in hexanes.

Attempt 18

0.3528 g of product VI is introduced directly into the reactor at 90 ° C. The reactor is charged with 1 liter of isobutane and then ethylene is introduced up to a pressure of 100 psi. No consumption of ethylene was detected. Therefore 2.0 ml of a 1M TEA in hexanes solution was introduced into the reactor. Only then will ethylene be consumed.

- 88 P o k s 19

0.3482 g of product VI is introduced directly into the reactor at 90 ° C. 2.0 ml of a TEA solution in hexanes was also added after the reactor before introducing 1 liter

isobutane. Ethylene was then introduced into the reactor up to a pressure of 100 psi. Since ethylene does not start to be consumed, hydrogen gas up to 0.21 MPa is introduced into the reactor. Only then will ethylene be consumed.

The data presented in Table XVI show that the chromium compounds of the invention can be used for polymerization and / or trimerization of olefins either on a support (experiments 1 to 16) or without a support (experiments 17 to 19). In addition, the conditions may be varied to increase the amount of trimmer (Trials 1 to 5 and 9) or to increase the yield of the solid product, i.e. the polymer (Trials 6, 7 and 13). Experiments 1 and 3 'show that high activity can be achieved.

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lower than the actual value. The actual value is probably about 2000.

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-32Example IX

All polymerization experiments were carried out as described in Example VIII.

The density is determined in g.cm @ -1 on a compression molded sample which has been cooled at a rate of about 15 ° C per hour and tempered for about 4 hours at room temperature in accordance with ASTM D 1505 and ASTM D 1928, conditin C. Index The high load melt flow rate (HLMI) is determined according to ASTM D 1238 at 190 ° C using a weight of 21.6 g. The melt flow rate (MI) is determined according to ASTM D 1238 at 190 ° G using a weight of 2.160 g. .

- 93 Experiment 20

0.100 g of product V (prepared in tetrahydrofuran as solvent) was heated at 80 ° C for 4 hours under a stream of nitrogen to remove the residue of tetrahydrofuran and then suspended in 15 ml of ambient temperature toluene. 7.0 ml of a triethyl aluminum solution in hexanes is added to the mixture and the solution is stirred for 24 hours, immediately after the addition of triethyl aluminum, a brown solution is formed and the product V is completely dissolved. (4) (2.0 g) and stirred for 2 hours The supported catalyst in the form of a brown solid is filtered from the solution, washed twice with toluene and then twice with pentane, 0.225 g of this catalyst is mixed with 0.078 g of chromium catalyst When mixed, both components are in the form of a free-flowing powder and the chromium catalyst supported on tergel is prepared as described in U.S. Pat. catalyst mixture directly brought into the polymerization reactor. After the introduction of the catalyst, but before adding isobutane (reaction solvent) to the reactor was added 3.0 ml of 0.5% solution of triethylaluminum in heptane to remove impurities from the feed. Ethylene was introduced into the reactor up to an overpressure of 100 psi. After 60.8 minutes, 190 g of polymer are formed. The polymer has an MI of 6.5 g / 10 min, an HLMI of 366.2 g / 10 min and a density of 0.0132 g / cm. Catalyst activity was 730 g polymer / g catalyst / hr based on experiment time of 60.8 min. The test temperature is

- 94 Experiment 21

0.100 g of product V (prepared in tetrahydrofuran as solvent) was heated at 80 ° C under a stream of nitrogen for 4 hours to remove it; residue of tetrahydrofuran and then suspended in 15 ml of toluene at ambient temperature. To the mixture was added 7.0 mL of a 1M solution of triethyl aluminum in hexanes, and the solution was stirred for 24 hours. Immediately after the addition of triethyl aluminum a brown solution formed and the product V completely dissolved. AlPO4 aluminophosphate (P / Al molar ratio = 0.4) (2.0 g) was added to the solution, and the mixture was stirred for 2 hours. The supported catalyst as a brown solid was filtered from the solution, washed twice with toluene and then twice with pentane. 0.2314 g of this catalyst is mixed with 0.0184 g of a titanium-containing catalyst. When mixed, both components are in the form of a free-flowing powder. The titanium-containing catalyst is prepared as described in U.S. Pat. Nos. 4,325,837 and 4,326,988, using ethyl aluminum dichloride as the aluminum alkyl compound. The resulting catalyst mixture (0.2385 g) was fed directly into the polymerization reactor. After introduction of the catalyst but before the addition of isobutane (1 liter, reaction solvent), 3.0 ml of a 0.5% solution of triethyl aluminum in heptanes was added to the reactor to remove impurities from the feed. Then the reactor was brought molecular hydrogen (H ₂₎ up to a pressure of 343.5 psig ethylene until an overpressure of 3.78 MPa. After 31.0 minutes, 82 g of polymer are formed.

The polymer has an MI of 0.011 g / 10 min, an HLMI of 0.63 g / 10 min and a density of 0.9429 g / cm &lt; 3 &gt;. The catalyst activity is 670 g polymer / g catalyst / h based on experiment length 31, 0 minutes. The test temperature is 90 ° C, the total overpressure is 3.73 MPa.

In the foregoing examples, the invention has been described in detail on its specific aspects. The invention is not limited to these aspects, and only the following definitions are to be construed as limiting the scope thereof.

Claims (10)

PATENT CLAIMS 1. A process for the polymerization of olefins, characterized in that the polymerization is carried out in the presence of a polymerization catalyst and a cocatalyst prepared by a process comprising forming a mixture of (i) a chromium salt, (b) a metal amide and (c) ether. or a catalyst comprising titanium and / or vanadium. The process according to claim 1, wherein the cocatalyst is a chromium compound selected from the group consisting of compounds of formula Cr ₅ (C ₄ H ₄ N) ₁₀ (C ₄ H ₈ O) ₄ , Cr (C ₄ H ₄ N) _4, [Cr (C ₄ H ₄ N) _4] [Na] ₂ .2 (OC ₄ H _8), [Cr (C ₄ H ₄ N) ₅ (OC ₄ H _8)] [ Cr (C ₄ H ₄ N) ₅ (OC ₄ H ₈ )] [Na] ₂ .4 (OC ₄ H ₈ ) and mixtures thereof. 3. The process according to claim 1, wherein a cocatalyst supported on an inorganic oxide is used as the carrier. 4. A process according to claim 1, wherein olefins containing 2 to 30 carbon atoms in the molecule are used. 5. The process according to claim 4, wherein olefins selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene and mixtures thereof are used. 6. The process according to claim 5, wherein the olefin is predominantly ethylene. 7. The process of claim 1 wherein the polymerization is carried out at a temperature in the range of from about 66 DEG C. to about 110 DEG C. 8. The process of claim 1 wherein hydrogenation is present during the polymerization. 9. The process of claim 1 wherein the polymerization is carried out by a slurry process. 10. The process of claim 1 wherein the olefin is ethylene and the polymer is isolated at a density of 0.9 to 0.93 g.cm &^lt; ^{-3 &gt};.