Novel organonickel sigma-complex - ethylene oligomerisation precatalyst

FIELD: chemistry.

SUBSTANCE: invention relates to an organonickel sigma-complex of formula ([NiBr(Xy)(bpy)], where Xy=2,6-dimethylphenyl, bry=2,2'-bipyridyl). Said complex exhibits high catalytic activity during oligomerisation of ethylene with retention of good solubility in carbon solvents.

EFFECT: possibility of oligomerisation in completely homogeneous conditions.

2 cl, 7 ex, 1 tbl, 1 dwg

 

The invention relates to the chemical industry, in particular to the creation of new michelangelesque catalysts, namely to a new connection - nickilorenicki Sigma-complex - 2,6-dimetilfenil-2,2'-bipyridyl-nickelbased ([NiBr(Xy)(bpy)], where Xy=2,6-dimetilfenil, bpy=2,2'-bipyridyl), which can be used in the catalytic oligomerization of ethylene, leading to the formation of alpha-olefins (oligomers of ethylene) fractions C4-C12, and as a reagent for the introduction of the aromatic fragment in the reaction cross-combination of organic halides, mono-, di-, trichlorophenol.

Known precatalysts the oligomerization of ethylene type Brookhart based on complexes of Nickel bromide with diimine ligands [C.M.Killian, L.K.Johnson, M.Brookhart. Preparation of linear α-olefins using cationic nickel(II) α-diimine catalysts. Organometallics. 1997. 16. 2005-2007]. However, these compounds are insoluble in hydrocarbon solvents such as toluene, benzene, aliphatic limit and unsaturated hydrocarbons, which fails to achieve the homogeneity of the solution of the above precatalyst, which severely limits the possibility of their wide industrial applications (the problem of transporting the suspension of precatalysts in the flowsheet).

Known [RU 2202413 C1, 2003.04.20] catalysts based on Nickel to obtain dimers and oligomers of olefins fraction 2-C6. The catalyst consists of a compound of Nickel deposited on a polymer base, swelling in the solvent, which is selected chain rubber mesh structure with swelling properties in hydrocarbon solvent of 0.1 to 4.5 ml/g of catalyst at a molar ratio of aluminum to Nickel 1-5 and the Nickel content of 0.2-2.2 wt.%; and activator - alyuminiiorganicheskikh connection. The catalyst additionally contains a waxy paraffin or olefin, is applied in the form of a film on the surface of the catalyst.

The disadvantages of this catalyst is a rather complicated procedure of its preparation, which is implemented in the molding or foaming, with the formation of sheets, films, pellets, as well as by extrusion with obtaining fibers, pipes, sausages, and low stability with respect to oxygen, which requires additional protection measures implemented through the processing of the waxy paraffin and / or olefin.

Described [EN 2005106204 A, 2006.03.20] a number of transition metal complexes of General formula (I, Ia, Ib) for the oligomerization of olefins:

in which M denotes an atom of Nickel, palladium or platinum; L1represents a ligand, at least one depleted in electrons dual-ol is fineway communication; a L2represents a monodentate carbene ligand of the formula (II) or formula (III)

However, these complexes include unstable Kurbanova ligands, are inclined to the process of dimerization and interaction with the organic substrates.

Described [EN 2287513 C2, 2006.11.20] the composition is effective Nickel-containing catalyst for oligomerization of ethylene, obtained by reacting in a polar organic solvent in the presence of ethylene:

a) simple salts of divalent Nickel;

b) a reducing agent on the basis of boron hydride;

a) a water-soluble base;

d) a ligand selected from o-dihydrocarbamazepine acids and their alkali metal salts;

e) trivalent phosphite.

Disadvantages of the proposed solution is the use of only polar solvents, recovery of reagent-based hydrides of boron) as an integral component of the catalytic system and the additional chemical compounds (phosphites and water-soluble base to maintain the pH, which significantly increases the cost of the proposed catalyst.

Known [RU 2301791 C2, 2007.06.27] catalytic system for carrying out the oligomerization of ethylene, which use complex of Nickel(0) [Ni(PPh3)4] the combination with efratom of boron TRIFLUORIDE (BF 3·OEt2), styrene and methyl methacrylate (MMA) at molar ratios of Ni(PPh3)4:(BF3·OEt2):styrene: MMA=1:5:0,5-2:0,5-2.

The main disadvantage of the proposed system is the low conversion of ethylene and the yields of products of oligomerization (the ratio of oligomers in the mixture - C4-37%, C6-6% and C8-57%), and isomerization products of oligomerization and low stability of the complex of Nickel(0) [Ni(PPh3)4] in the catalytic process in the presence of BF3·OEt2accompanied by the formation of Nickel fluoride during the catalytic process and leading to deactivation of the catalyst.

The closest analogue of the claimed complex [NiBr(Xy)(bpy)] is the σ-complex [NiBr(Mes)(bpy)] (Mes=2,4,6-trimetilfenil), first obtained by Idelem in 1985 [W.Siedel. // Zeitschrift für Chemie 1985. 25(11). 411] the reaction of the ligand exchange from the corresponding complex [NiBr(Mes)(PPh3)2] and subsequently improved by the method of Klein in 2001 [A.Klein. // Z.Anorg. Allg. Chem. 2001. 627(4). 645-650].

The complex [NiBr(Mes)(bpy)] showed catalytic activity in the oligomerization of ethylene in the presence of methylalumoxane (MAO), as the activating reagent [D.Yakhvarov, D.Tazeev, O.Sinyashin, G.Giambastiani, C.Bianchini, A.M.Segarra, P.Lönnecke, E.Hey-Hawkins. II Polyhedron. 2006. 25. 1607-1612].

Object of the invention is a new michelangelesque Sigma-complex - precatalysts oligomerization ethyl is on, extends the range of known catalysts specified destination.

The goal of the project is achieved by the invention, namely the new connection - 2,6-dimetilfenil-2,2'-bipyridyl-nickelbased

([NiBr(Xy)(bpy)], where Xy=2,6-dimetilfenil, bpy=2,2'-bipyridyl).

The technical result of the invention is a new michelangelesque Sigma-complex - 2,6-dimetilfenil-2,2'-bipyridyl-nickelbased ([NiBr(Xy)(bpy)], where Xy=2,6-dimetilfenil, bpy=2,2'-bipyridyl)exhibiting higher catalytic activity in the oligomerization of ethylene compared to the prototype with the continued good solubility in hydrocarbon solvents, which allows oligomerization in a completely homogeneous conditions.

The technical result is achieved due to the presence in the structure nicolangelo complex of di-ortho-substituted aromatic fragment containing two methyl groups as substituents. The presence of such substituents prevents rotation of the aromatic fragment around a Sigma-bond to the Nickel-carbon, thereby giving stability consider nickilorenicki Sigma-complex.

The distinguishing characteristics of compounds [NiBr(Xy)(bpy)] from the prototype complex [NiBr(Mes)(bpy)] is the presence of two methyl substituents in the Sigma-linked aromatic the fragment, that significantly increases the catalytic activity of the Sigma-complex in the oligomerization of ethylene. At the same time maintaining good solubility in hydrocarbon solvents, which allows oligomerization in a completely homogeneous conditions.

The inventive complex are similar [NiBr(Mes)(bpy)] by a modified method [A.Klein. // Z.Anorg. Allg. Chem. 2001. 627 (4). 645-650] with yields up to 83%.

The retrieval process includes the following stages:

1. Obtaining solution magyarkanizsa connection [XyMgBr] (Xy=2,6-dimetilfenil) by well-known methods [U.Luening, C.Wangnick, K.Peters, H.G. von Schnering // Chem.Ber. 1991. 124. 397].

2. Synthesis nicolangelo complex [NiBr(Xy)(PPh3)2] the interaction of a solution of complex [NiBr2(PPh3)2] in a suitable organic solvent (e.g. tetrahydrofuran (THF)) and magyarkanizsa connection [XyMgBr] in an organic solvent (e.g. diethyl ether) and the selection range of conventional techniques.

3. Synthesis nicolangelo complex [NiBr(Xy)(bpy)] the interaction of the complex [NiBr(Xy)(PPh3)2] with a slight excess 2,2'-bipyridyl in THF under stirring for several hours at a temperature of 50°C and the allocation of the received complex known techniques.

Received michelangelesque complex tested for catalytic activity in the process of oligomerization of ethylene similarly [D.Yakhvarov, D.Tazeev, O.Sinyashin, G.Giambastiani, C.Bianchini, A.M.Segarra, P.Lönnecke, E.Hey-Hawkins. // Polyhedron. 2006. 25. 1607-1612]. Comparison of catalytic activity with the prototype shows that the claimed complex [NiBr(Xy)(bpy)], containing two methyl substituent in the aromatic fragment has a higher catalytic activity in the oligomerization of ethylene in the presence of MAO as the activating reagent.

To illustrate the invention, examples of receipt of the proposed complex, its physico-chemical characteristics and the results of the study of catalytic activity of the claimed compounds.

Description of the synthesis nicolangelo complex [NiBr(Xy)(bpy)]

Example 1

Synthesis nicolangelo complex [NiBr2(PPh3)2]

To a suspension containing 6.5 g (0,0297 mol) of anhydrous Nickel bromide in 100 ml of dry THF, was added dropwise 70 ml of a solution of 15.5 g (0,0592 mol) of triphenylphosphine in THF. The solution is stirred for 5 hours at 40°C. then the solvent is distilled off, and dry the residue under vacuum (18 mm Hg), washed with diethyl ether (2 times × 30 ml) and dried in air for 12 hours.

Received 20,0 g of complex [NiBr2(PPh3)2] (yield 90%).

Found: C, 59.07; H, 4.34; P 8.69; Ni 7.24%;

Calculated for C36H30Br2P2Ni (Mw: 743.82 g mol-1): C, 58.13; H, 4.07; P 8.33; Ni 7.89%.

31P-NMR (162 MHz, DMF 25°C): δ=25.30 (singlet).

Example 2

Synthesis nicolangelo complex [NiBr(Xy)(PPh3)2]

To a solution of 20.0 g (0,0269 mol) complex [NiBr2(PPh3)2] in 600 ml of THF was added dropwise to 28.2 ml of 1 M solution magyarkanizsa connection [XyMgBr] (5.9 g, 0,0282 mol) in diethyl ether at room temperature. After addition of the total volume of the solution magyarkanizsa connection, the reaction mixture is boiled for 2 hours. Then to the reaction mass Pocatello add 50 ml of an aqueous solution of ammonium chloride, is stirred, the aqueous layer was separated with a separating funnel, washed the remaining organic layer with water (3 times×50 ml) and dried the organic layer over magnesium sulfate. After that, the solvent is distilled off in a water jet vacuum pump (18 mm Hg). The residue is recrystallized from toluene.

Received 17,6 g nicolangelo complex [NiBr(Xy)(PPh3)2] (M=768) (yield 85%).

Found: C, 69.13; H, 5.73; P 8.21; Ni 7.98%.

Calculated for C36H30Br2P2Ni (Mw: 768.33 g mol-1): C, 68.78; H, 5.12; P 8.06; Ni 7.64%.

31P-NMR (162 MHz, C6D6, 25°C): δ=18.13 (singlet).

Example 3

Synthesis nicolangelo complex [NiBr(Xy)(bpy)]

To a suspension containing 17.6 g (0,0229 mol) complex [NiBr(Xy)(PPh3)2] in 180 ml of THF added to 3.73 g (0,0239 mol) 2,2'-bipyridyl dissolved in 100 ml of THF. The resulting mixture peremeshivayu for three hours at 50°C. After that, THF evaporated and washing the residue with diethyl ether (3 times 30 ml). By recrystallization from toluene solution obtain 7.6 g of complex [NiBr(Xy)(bpy)] (yield 83%).

Crystals of the complex [NiBr(Xy)(bpy)] for x-ray analysis is obtained by recrystallization from THF.

Characteristics of the proposed complex of 2,6-dimetilfenil-Nickel(II)-bromide-2,2'-bipyridyl ([NiBr(Xy)(bpy)]):

1H-NMR (400 MHz, THF-d8, 25°C): δ=9.31 (d, 1H, bpyH6,3JH6H5=5.70 Hz); 8.16 (d, 1H, bpyH3,3JH4H3=7.90 Hz); 8.09-8.14 (m, 2H, bpyH3', bpyH4,3JH4H3=7.90 Hz,3JH5H4=7.30 Hz); 8.05 (m, 1H, bpyH4; 7.60 (dd, 1H, bpyH5,3JH6H5=5.70 Hz,3JH5H4=7.30 Hz); 7.28 (d, 1H, bpyH6',3JH6'H5'=5.40 Hz); 7.18 (m, 1H, bpyH5',3JH6'H5'=5.40 Hz); 6.55 (s, 3H, HXy); 3.08 (s, 6H, o-CH3).

Found: C, 54.37; H, 4.81; N, 7.26%.

Calculated for C18H17BrN2Ni (Mw: 399.94 g mol-1): C, 54.06; H, 4.28; N, 7.00%.

Tpl.139°C (decomp. 152°C).

The structure of the complex [NiBr(Xy)(bpy)] in the crystal is shown in figure 1 is monoclinic, P2(1)/c, Z=4, a=893.1(5) pm, b=1197.0(5) pm, c=1755.6(5) pm, α=90.000(5)°, β=91.072(5)°, γ=90.000(5)°.

Study of catalytic activity of the complex [NiBr(Xy)(bpy)] (complex 1) and comparison with the catalytic activity of the complex [NiBr(Mes)(bpy)] (complex 2)

Example 4

A portion of the complex (4.8 mg, 12 the mole) [NiBr(Xy)(bpy)] vaccum (1.6·10 -3mm Hg) in an autoclave with a volume of 500 ml within 3 hours. After that, the autoclave was added 100 ml of toluene containing (3600 mol) MAO, prepared by adding 2.37 ml of a commercially available solution of MAO (10% solution in toluene, Aldrich) to 97.63 ml of toluene. After stirring the reaction mixture at room temperature for a few seconds in the autoclave create a pressure of 5 ATM ethylene and leave the reaction mixture with stirring under pressure for 15 minutes then autoclave is cooled to -10°C, relieve pressure and ethylene added to the reaction mixture of 2 ml of 5% HCl solution in methanol to neutralize the excess MAO and stop the catalytic process. Analysis of the obtained products of oligomerization in the reaction mixture is performed by gas chromatography. The results of catalytic tests are shown in table 1 (experiment 1).

Example 5

The process is carried out under the conditions of example 4, but using a portion of the complex [NiBr(Xy)(bpy)] 0.5 mg (1,2 mol). The results are shown in table 1 (experiment 2).

Example 6

The process is carried out under the conditions of example 4, but as precatalysts use complex [NiBr(Mes)(bpy)] (experiment 3).

Example 7

The process is carried out under the conditions of example 5, but using the complex [NiBr(Mes)(bpy)] (experiment 4).

The results of the experiments is shown in table 1. The conversion of ethylene was calculated based on the weight of ethylene, which came in reaction (on the weight gain of the autoclave during the catalytic process and on the basis of gas chromatography of the reaction mixture with internal standard), and a constant Schulz-Flory (α) is determined on the basis of the average molar ratio of the C6, C8 and C10 fractions obtained olefins. As shown by the results of the catalytic tests (table 1), the conversion of ethylene in experiment 1 when using complex 1 is equal to 9.72 g (the ratio of oligomers in the mixture of C4 - 5.17 g; C6 - 2.60 g; C8-1.16 g; C10 - 0.49 g; C12 - 0.20 g, α=0.335), which significantly exceeds the conversion of ethylene using prototype - complex 2 - 6.93 g (the ratio of oligomers in the mixture of C4 - 3.49 g; C6 - 1.87 g; C8 - 0.89 g; C10 - 0.40 g; C12 - 0.17 g; α=0.357). The change in the ratio of complex/MAO (experiments 2 and 4) reduces the conversion of ethylene in the catalytic process, but also shows higher catalytic activity of complex 1 (0.75 g conversion of ethylene; C4 - 0.39 g; C6 - 0.20 g; C8 - 0.09 g; C10 - 0.04 g; C12 - 0.02 g, α=0.342) in relation to the prototype - complex 2 (0.56 g conversion of ethylene; C4 - 0.26 g; C6 - 0.15 g; C8 - 0.08 g; C10 - 0.04 g; C12 - 0.02 g, α=0.390).

As can be seen from the table, the proposed complex has a higher catalytic activity in comparison with the known prototype - complex [NiBr(Mes)(bpy)].

Thus declared the new dikelola the practical complex precatalysts oligomerization of ethylene, which extends the range of known catalysts specified purposes that in the presence of an activating reagent effectively oligomerizate ethylene olefins in the C4-C12 range, and carry out the process in homogeneous conditions.

The catalytic activity of the complexes [NiBr(Xy)(bpy)] (1) and [NiBr(Mes)(bpy)] (2) in the presence of MAO
No.ComplexAspect]-e complex /MAOThe conversion of ethylene, gWeight oligomers, gα
C4C6C8C10C12
1112/ 36009.725.172.601.160.490.200.335
211.2/ 36000.75 0.390.200.090.040.020.342
3212/ 36006.933.491.870.890.400.170.357
421.2/ 36000.560.260.150.080.040.020.390

1. Michelangelesque Sigma-complex of the formula [NiBr(Xy)(bpy)], where Xy=2,6-dimetilfenil, bpy=2,2'-bipyridyl.

2. Michelangelesque Sigma-complex according to claim 1 as precatalysts oligomerization of ethylene.



 

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FIELD: composition and structure of composite metal semiconductor meso-porous materials; titanium-dioxide-based catalyst for photo-chemical reactions.

SUBSTANCE: proposed catalyst is meso-porous titanium-dioxide-based material containing crystalline phase of anatase in the amount no less than 30 mass-% and nickel in the amount no less than 2 mass-%; material has porous structure at average diameter of pores from 2 to 16 nm and specific surface no less than 70 m2/g; as catalyst of photo-chemical reaction of liberation of hydrogen from aqua-alcohol mixtures, it ensures quantum reaction yield from 0.09 to 0.13. Method of production of such catalyst includes introduction of precursor - titanium tetraalkoxyde and template of organic nature, holding reagent mixture till final molding of three-dimensional structure from it at successive stages of forming sol, then gel, separation of reaction product and treatment of this product till removal of template; process is carried out in aqua-alcohol solvent containing no more than 7 mass-% of water; at least one of ligands is introduced into solvent as template; ligand is selected from group of macro-cyclic compounds containing no less than four atoms of oxygen and/or from complexes of said macro-cyclic compounds with ions of metals selected from alkaline or alkaline-earth metals or F-metals containing lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium; mixture is stirred before forming of sol maintaining its temperature not above 35°C till final molding of three-dimensional structure from reagent mixture; mixture is held in open reservoir at the same temperature at free access of water vapor; after removal of template from three-dimensional structure, mixture is first treated with nickel salt solution during period of time sufficient for withdrawal of nickel ions from solution by pores of structure, after which is it kept in hydrogen-containing medium during period of time sufficient for reduction of nickel ions in pores of structure to metallic nickel.

EFFECT: enhanced sorption and photo-catalytic parameters; reproducibility of catalyst properties.

7 cl, 68 ex

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