Novel iridium-platinum complex and preparation method thereof

FIELD: chemistry.

SUBSTANCE: invention relates to an iridium-platinum complex of formula (I) , where Cp* is selected from a group consisting of a cyclopentadienyl ligand, pentamethylcyclopentapentadienyl ligand, pentaethylcyclopentadienyl ligand and pentapropylcyclopentadienyl ligand, X is a hydrogen atom or a substitute group selected from a group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and an organic group located in the ortho, meta or para position relative the phenyl group or a combination of these positions, and Y is selected from a group consisting of a methyl group, an ethyl group and a propyl group, wherein said organic group is selected from a group consisting of an alkyl group, alkoxy group, alkenyl group, alkenyloxy group, alkynyl group, alkynyloxy group, aryl group, aryloxy group, aralkyl group and an aralkyloxy group, which can have a heteroatom or an ether bond, which are substituted or unsubstituted and which are C1-C30 The invention also discloses a method for synthesis of the iridium-platinum complex.

EFFECT: invention enables preparation of an iridium-platinum complex capable of giving iridium-platinum clusters, having a controlled cluster size and controlled alloy composition

3 ex, 1 dwg, 10 cl

 

The technical field to which the invention relates

The present invention relates to iridium-platinum complex and method of its production.

Prior art

According to the study in recent years, metal clusters with adjustable size, differ from compact metal by chemical properties such as catalytic activity, and physical properties such as magnetic properties.

The method of synthesis of metal clusters with a simple adjustable size and in the quantity necessary for use of the distinctive properties of clusters. Moreover, currently known method of producing metal clusters with adjustable size, is as follows: the metal target is evaporated in vacuum to form clusters with different sizes; the resulting clusters are separated by cluster size, using the principle of mass spectrometry. However, using this method, it is impossible to synthesize metal clusters with a simple adjustable size, and in great numbers.

The distinctive properties of metal clusters described, for example, in the reference: M. Ichihashi et al., "Adsorption and Reaction of Methanol Molecule on Nickel Cluster Ions, Nin+ (n = 3-11)," J. Phys. Chem., A, 104,11885 (2000) [1]. As shown in figure 1 of this work, the reaction method is the outer coat of the platinum catalyst with molecules of methane in the gas phase is strongly influenced by the size of the platinum cluster, this is the cluster size, optimal for the reaction.

Embodiments of applications of the catalytic activity of the noble metal include purification of exhaust gas emitted from an internal combustion engine such as an automobile engine. During the purification of exhaust gas carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOx) and the like contained in the exhaust gas into carbon dioxide, nitrogen and oxygen catalytic component, the main component of which is a noble metal such as platinum (Pt), rhodium (Rh) and iridium (Ir). With respect to the exhaust gas catalytic component, which is a noble metal, usually printed on active media, such as aluminum oxide, to provide greater surface contact between the exhaust gas and the catalyst component.

Noble metal, which is a component of the catalyst is usually applied to the active medium by the following procedure: oxide carrier is impregnated with a solution of the nitrate salt of a noble metal or a solution of the complex of the noble metal with the atoms of one noble metal, so that the connection of the noble metal distributed on the surface of the oxide carrier; then impregnated with a solution of the carrier is dried and calcined. CL is firewood noble metal, having a given size or a given number of atoms, it is difficult to obtain by this method.

For such catalysts for purification of exhaust gas to further improve the activity of the exhaust gas, the proposed content of noble metal in a state of clusters. For example, Japanese publication of patent application, which was not examined, (Kokai) No. 11-285634 reveals that when used complex metal cluster carbonyl group as a ligand, a metal catalyst in a state of fine particles can be applied directly to the media. In addition, the Japanese publication of patent application, which was not examined (Kokai) No. 2006-055807, reveals that the noble metal forming the multi-complex, can be deposited on the oxide carrier deposition of multi-core complex containing a noble metal, and removing the organic substance constituting the multi-complex.

In addition, the Japanese publication of patent application, which was not examined (Kokai) No. 9-253490, reveals that the metal clusters, made of alloy, forming a solid solution with rhodium and platinum, obtained by adding a recovery agent to the solution containing the ion of rhodium and platinum ion. As described in the reference, and is known, the alloy forms a solid solution with rhodium and platinum, exhibits properties different from the properties of one of rhodium and one platinum.

As described in the above references, it is known the use of clusters of noble metal alloys, noble metal in the field of catalysts. However, none of the references disclose obtain clusters of noble metal, with adjustable size and adjustable composition of the alloy.

Therefore, the aim of the present invention to provide a new iridium-platinum complex, able to give iridium-platinum clusters with adjustable cluster size and adjustable composition of the alloy, and its production method.

Disclosure of invention

Iridium-platinum complex according to the present invention has the following formula (I):

where Cf* is selected from the group consisting of cyclopentadienyls ligand pentamethylcyclopentadienyl ligand pentamethylcyclopentadienyl ligand and pentabromoethylbenzene ligand, X represents a hydrogen atom or a group substituent selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group and organic groups that are located in the ortho-, meta - or paraprotein relative to the phenyl group, or a combination of these the provisions and Y is selected from the group consisting of methyl group, ethyl group and through the group.

Because iridium and platinum are directly connected together within iridium-platinum complex of the present invention, the clusters iridium-platinum alloy having an atomic ratio of Ir/Pt, is equal to 2/1, can be obtained by removing forming complex organic matter by ignition or a similar method.

The method of obtaining iridium-platinum complex of the present invention involves the following stages:

(a) providing a compound of the following formula (II):

[Cp*Ir(µ2-NPh-X)]2(II)

where Cp* is selected from the group consisting of cyclopentadienyls ligand pentamethylcyclopentadienyl ligand pentamethylcyclopentadienyl ligand and pentabromoethylbenzene ligand, Ph represents a phenyl group and X represents a hydrogen atom or a group substituent selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group and organic groups that are located in the ortho-, meta - or paraprotein relative to the phenyl group, or a combination of these provisions;

(b) providing a compound of the following formula (III):

[PtY22-SZ)]2(III)

where Y is selected from the group consisting of methyl group, ethyl group propileno group, and Z is selected from the group consisting of methyl group, ethyl group and through the group; and

(C) mixing the compounds of formula (II) and compounds of formula (III) in solution.

According to the method according to the present invention can be obtained iridium-platinum complex of the present invention.

Brief description of drawing

The drawing is a graph selected from references 1 and showing the relation between the size of the Pt cluster and reactivity.

The best way of carrying out the invention

(Iridium-platinum complex)

Iridium-platinum complex of the present invention has the following formula (I):

where Cf* is selected from the group consisting of cyclopentadienyls ligand pentamethylcyclopentadienyl ligand pentamethylcyclopentadienyl ligand and pentabromoethylbenzene ligand, X represents a hydrogen atom or a group substituent selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group and organic groups that are located in the ortho-, meta - or paraprotein relative to the phenyl group, or a combination of these provisions, and Y is selected from the group consisting of methyl group, ethyl group and through the group, particularly a methyl group.

As explained above, to Asteri iridium-platinum alloy, having the atomic ratio of Ir/Pt, is equal to 2/1, can be obtained by removing forming complex organic substances by annealing or similar methods, in particular by impregnation of the support with a solution containing the complex, and thermal drying of the solution.

Examples of the organic group is used as the group X in the iridium-platinum complex according to the invention include organic group selected from the group consisting of alkyl groups, alkoxygroup, alkenylphenol group, alkenylacyl, alkenylphenol group, alkyloxy, aryl group, alloctype, aranceles group and aralkylated, which may have a heteroatom, or a simple relationship ether, which are substituted or unsubstituted and which are1-C30(namely from 1-30 carbon atoms (below is used with the same meaning), for example, organic groups With1-C10.

In particular, examples of the organic group is used as the group X in the iridium-platinum complex according to the invention include organic group selected from the group consisting of alkyl groups, alkoxygroup, aryl group, alloctype, aranceles group and aralkylated that represent1-C30in particular1-C10.

Some examples of alkyl gr is PPI include methyl group, ethyl group, n-sawn group, isopropyl group, n-boutelou group, isobutylene group, sec-boutelou group, tert-boutelou group, n-pentelow group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropylene group, cyclopentyloxy group, n-hexoloy group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylethylene group, 1,1,2-trimethylethylene group, 1-ethyl-2-methylpropyloxy group, tsiklogeksilnogo group, n-heptylene group, 2-methylhexanoic group, 3-methylhexane group, 4-methylhexanoic group, 5-methylhexanoic group, 2,4-dimethylpentyl group, n-aktiline group, 2-ethylhexyloxy group, 2,5-dimethylhexane group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexane group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexanoyl group, n-naniloa group, n-decile group, 4-atrakcyjny group, and 4-ethyl-4,5-dimethylhexanoic group.

Some examples of alkoxygroup include alkoxygroup, arr is organised by the accession of the oxygen atom to the end one atom of the above alkyl groups.

Some examples of aryl groups include phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tert-butylaniline group, 1-naftalina group and 2-naftalina group.

Some examples of alloctype include alloctype formed by the joining of the oxygen atom to the end atom of one of the above aryl groups.

Some examples aranceles group include benzyl group, fenetylline group, α-methylbenzyl group, α,α'-dimethylbenzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, furfuryl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 4-ethylbenzyl group, 4-isopropylbenzyl group and 4-tert-butylbenzyl group.

Some examples of aralkylated include aralkylated formed by the joining of the oxygen atom to the end atom of one of the above Uralkalij groups.

For iridium-platinum complex for us is oedema invention X may be a hydrogen atom or a group of Deputy posted in paraprotein relative to the phenyl group. This location group X is preferred because the spatial shortness of group X prevents destabilization of the complex. For example, X may be a nitrogen atom, a bromine atom, or benzyloxypropionic placed in paraprotein relative to the phenyl group.

Drying and curing solution containing iridium-platinum complex of the present invention, can be carried out at a temperature and for a time sufficient to obtain metal and metal oxide clusters. For example, the solution is dried at temperatures of from 120 to 250°C for 1-2 hours, and then utverjdayut at temperatures from 400 to 600°C. for 1-3 hours. Any solvent may sustain iridium-platinum complex according to the invention, for example an organic solvent, such as tetrahydrofuran, can be used as the solvent for the solution used in the method.

Examples of the catalyst carrier, which is used in the production of catalyst carrier using complex metal according to the invention include porous metal oxide media selected from the group consisting, for example, aluminum oxide, cerium oxide, zirconium oxide, silicon oxide, titanium oxide, magnesium oxide and op is Tania these carriers.

Although iridium-platinum complex of the present invention can be obtained by any method, it can be properly obtained by the method according to the invention, explained below.

(Method of obtaining iridium-platinum complex)

The method of synthesis of iridium-platinum complex of the present invention includes the following stages:

(a) providing a compound of the following formula (II):

[Cp*Ir(µ2-NPh-X)]2(II)

where Cp* is selected from the group consisting of cyclopentadienyls ligand pentamethylcyclopentadienyl ligand pentamethylcyclopentadienyl ligand and pentabromoethylbenzene ligand, Ph represents a phenyl group, and X represents a hydrogen atom or a group substituent selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group and organic groups that are located in the ortho-, meta - or paraprotein relative to the phenyl group or the combination of these provisions;

(b) providing a compound of the following formula (III):

[PtY22-SZ)]2(III)

where Y is selected from the group consisting of methyl group, ethyl group and through the group, and Z is selected from the group consisting of methyl group, ethyl group and through the group; and

(C) mixing the compounds of formula (II) and compounds of formula (III) in which aStore.

For groups X and Y in the way of getting iridium-platinum complex according to the present invention can be referenced for clarification about iridium-platinum complex of the invention.

The method of obtaining iridium-platinum complex according to the present invention may further include the formation of crystals iridium-platinum complex at concentration and cooling of the mixture in the form of a solution obtained in stage (C) (stage (d)).

The present invention is explained below by putting the links to the examples. However, these examples are intended only to explain the invention, and the present invention does not limited to.

In examples 1-3, explained below, were synthesized compounds 1A-1C.

Compounds 1A-1C represented by the following formula:

where Cp(IU)* represents pentamethylcyclopentadienyl ligand, X = N for compounds 1A, X = Br for compounds 1b and X = CH2Ph (where Ph is phenyl group) for compounds 1C.

Example 1. The synthesis of compounds 1A

Synthesis of compound 1A was performed according to the following methods (1)to(5). In addition, in the description of the following example, Cp(IU)* represents pentamethylcyclopentadienyl ligand, Ph represents a phenyl group, Me represents a methyl group, and Bu represents butyl the second group.

(1) Synthesis of [Cp(IU)*IrCl2]2

The synthesis of the compound was carried out according to the description of the link: R. G. Ball et al., "Synthesis and Structure of Dicarbonylbis(η-pentamehtylcyclopentadienyl)diiridium", Inorganic Chemistry, 29 (10), 2023-2025. This place made reference to the description of the link, and it is included in the description of this application.

Thus, the synthesis of compounds carried out as described below.

Pentamethylcyclopentadiene in excessive quantities (1.5 ml) was added to chloride of iridium (IrCl3·3H2O, 2.0 g, 5.4 mmol) in 50 ml obezhirennogo methanol. Thus obtained mixture was heated in a flask under reflux for 36 hours. The mixture was cooled to room temperature and the products were separated by filtration. The products were washed with methanol at room temperature. The formation of the upper layer liquid and the washing were combined and cooled at 0°C for 24 hours (the extracted amount of 2.0 g, yield 91%).

(2) Synthesis of Cp(IU)*IrN-t-Bu

The synthesis of the compound was carried out as described in the link: David S. Glueck et al., "Monomeric (Pentamethylcyclopentadienyl)iridium Imido Compounds: Synthesis, Structure, and Reactivity", J. Am. Chem. Soc., 113 (6), 2041-2054 (1991). This place made reference to the description of the link, and it is included in the description of this application.

Thus, the synthesis of the compound was carried out as described below.

[Cp(IU)*IrCl2]2(1,00 g of 1.26 mmol)obtained in the same way as in the above stage (1), LiNH-t-Bu (420 mg, 5,32 mmol) and stirred the third rod was introduced into a 100 ml flat-bottomed flask. THF (tetrahydrofuran) (50 ml) are condensed in a flat-bottomed flask at -196°C. the Flask was placed in an ice bath, and THF were thawed, while the content was stirred. The orange suspension was homogeneous within 5 minutes, and the solution changed color from dark brown to yellow. Volatiles were removed under reduced pressure, while the remainder was left in the flask. The rest, changing colour from brown to yellow, were extracted with pentane, and the solution was filtered through zerit on the Frit to obtain a solution, changing color from dark orange to yellow. The pentane was removed under reduced pressure to obtain a yellow powder in the amount of 914 g (yield 91%).

(3) Synthesis of [Cp(IU)*Ir(µ2-NPh)]2(or Cp(IU)*Ir(µ-NPh)2IrCp(IU)*)

The synthesis of the compound was carried out as described in the link: Daniel A. Dobbs, et al., "Synthesis and Reactivity of Bridging Imido and Imido-Oxo Complexes of Iridium. Water-Catalyzed and Uncatalysed Dimerization of Iridium Terminal Imido Complexes", Organometallics, 13 (11), 4594-605 (1994). This place made reference to the description of the reference material and it is included in the description of this application.

In other words, the synthesis of the compound was carried out as described below. Cf*IrN-t-Bu (228 mg, 0,572 mmol)obtained in the same manner as in the above stage (2), and benzene (15 ml) were placed in 25 ml flat-bottomed flask. To the solution was added aniline (55,1 mg, 0,592 mmol), and thus obtained solution premesis is whether at room temperature for 2 days. Volatiles were removed under reduced pressure 15 mtorr for 1 hour. Thus obtained black solution was dissolved in the minimum possible amount of toluene and the obtained crystals during formation of the layer with pentane. The solution was cooled to -40°C., to obtain black crystals (161 mg, 0,383 mmol, yield 67%).

(4) Synthesis of [Pt22-SMe)]2(or [{Pt2}2(µ-SMe2)2])

The synthesis of the compound was carried out as described in the link: Richard J. Puddephatt et al., "Synthesis Solution and Solid-State Structure (X-ray Analysis), and Some Reactions of the Dimer [PtMe3(µ-Ph2PCH2PPh2)]", J. Chem. Soc., Chem. Commun., (15), 805-806 (1981). This place made reference to the description of the link, and it is included in the description of this application.

In addition, the synthesis of compounds can be carried out according to the method described in "Bis(µ-dimethylsulfide)-Bis[dimethylplatinum]", Experimental Chemistry Series, 5th end., Vol. 21, 329-330, Maruzen, Tokyo (2004).

In other words, the synthesis can also be carried out by the method as described below.

K[PtCl4] + 2Me2S → CIS/TRANS - [PtCl2(SMe2)2] + 2KCl

CIS/TRANS - [PtCl2(SMe2)2] + 4MeLi → [{Pt2}2(µ-SMe2)2])+ 4LiCl + 2SMe2

500-ml flat-bottomed three-neck flask equipped with a magnetic rotor and membrane separation element and connected with the line of nitrogen so that nitrogen gas could be passed through the flask. To a solution of K[PtCl42)4][PtCl4] and CIS/TRANS-[PtCl2(SMe2)2] besieged in the form of a pink solid and a yellow solid. When the mixture was heated by the heater shell for 30 minutes, the whole pink product turns into yellow CIS/TRANS-[PtCl2(SMe2)2]. After cooling, the mixture 3 times were extracted with dichloromethane. The organic phase was dried over MgSO4. Then the mixture was filtered, and the filtered solution was concentrated under reduced pressure to obtain [PtCl2(SMe2)2] (CIS:TRANS = 1:2) as a bright yellow fine crystals, which are stable towards air and water (extracted number of 5,23-5.50 g, yield 87,4 - 92,0%).

The following reaction was carried out in dried nitrogen atmosphere with tube width, sufficiently dried by heating in vacuum immediately before use. 500 ml Schrenk tube, equipped with a membrane separation element, was placed a magnetic stirring rod, and a fine of CIS/TRANS-[PtCl2(SMe2)2] number 3,90 g (11.0 mmol) suspended in 160 ml of dehydrated ether. The mixture was cooled in an ice bath at 0°C. the Ice was placed in an ice ban is at the level of 3 cm above the liquid level so that the liquid was appropriately cool. The liquid for 10 minutes dripped MeLi solution (1.4 mol/l, the concentration galogensoderjasimi connection of 0.05 mol/l of 22.4 mmol) simple ether (16 ml). When the solution was stirred for 20 minutes after the dripping, then got a white suspension (when the solution became brown with stirring, then it is easily subjected to subsequent processing). To cause the hydrolysis, the reaction mixture was added saturated aqueous solution of ammonium chloride in quantities of 4 ml and 100 ml of distilled water, which was cooled to 0°C. Using 50 ml of simple ether, cooled to 0°C, the mixture 3 times were extracted. Pale yellow extracted liquid was dried over MgSO4at 0°C. To the extracted liquid was added a small amount (0.2 g) decolorizing charcoal, and after 5 minutes, the liquid was filtered. The solvent of the filtered solution was removed under reduced pressure (15 Torr)to obtain [{Pt2}2(µ-SMe2)2] in the form of a white solid. The extracted number was from 2.83 to 2.89 g (yield 89,6 is 91.5%).

(5) Synthesis of compounds 1A

All operations were carried out in nitrogen atmosphere. Tetrahydrofuran (THF) and hexane, individually, were distilled from sodium/benzophenone. Used deuterated Rast is oritel, frozen and obeshanniy 3 times and stored in the presence of molecular sieve 4 E.

THF solution (20 ml) [Pt2(µ-SMe)]2(307 mg, 0,534 mmol)obtained in the same manner as in the above stage (4)was added at room temperature to a THF solution (20 ml) of [Cp(IU)*Ir(µ2-NPh)]2(904 mg, of 1.077 mmol)obtained in the same way in the above stage (3). The mixture was stirred for 5 hours without further processing. The reaction solution was concentrated to approximately 10 ml concentrated solution of hexane were placed in a 25 ml, and the solution was allowed to stand at -20°C, to obtain the compound 1A (486 mg, 0,404 mmol, yield 37%) as a dark green plate crystals.

Thus obtained results of analysis of compound 1A were shaped as follows:

1H NMR (CDCl3)

δ: 7,3 (m, 8H, aryl), 6,9 (m, 2H, aryl), at 1.73 (s, 6H,2JPt-H= 87 Hz, Pt(IU)*2), to 1.38 (s, 30H, C5Me5).

13C NMR (CDCl3)

δ: 164,1, RUB 127.3, 123,9, 121,9 (aryl), 87,6 (C*5Me5), and 9.7 (C*5Me5), -7,4 (1JPt-c= 449 Hz, Pt*2).

FAB-MS (Mass spectrometry with fast atom bombardment)

(+)

m/z = 1062 (M+).

Elemental analysis

Analytically calculated for C34H46N2IrPt2·THF: C, 39,70; H, 4,59; N, 2,50.

Found: C, 40,10; H, 4,94; N, 2,35.

X-ray anal is C (Crystallographic data for 1A)

C38H54Ir2N2OPt, fW= 1134,32, orthorhombic space group Pbca, a = 16,521 (7), b = 20,669 (7), c = 21,945 (9) Å, V = 7494 (5) E3T = 29K, Z =8, µ (Mo-Kα) = 10,840 mm-1, 57588 measured reflections, 8117 only (Rint=0,0715), R1 = 0,0597, wR2 = 0,1416, GOF = 1,085.

Molecular structure of {Selected bond length (Ĺ) and angles (degrees)}

Irl-Ir2, 2,7693 (13); Ir1-Pt1, 2,6227 (9); Ir2-Pt1, 3,2214 (10); Ir1-N1, 2,057 (8); Ir1-N2, 2,046 (9); Ir2-N1, 2,006 (9); Ir2-N2, 2,007 (8); Pt1-N1, 2,143 (9); Pt1-N2, 2,151 (9); Pt1-C1, 2,046 (14); Pt1-C2, 2,069 (12); Ir2-Ir1-Pt1, 73,317 (19); Ir1-Ir2-Pt1, 51,249 (19); Ir1-Pt-Ir2, 55,43 (3); Ir1-N1-Ir2, 85,9 (4); Ir1-N1-Pt1, 77,3 (3); Ir2-N1-Pt1, 101,8 (4); Ir1-N2-Ir2, 86,2 (3); Ir1-N2-Pt1, 77,3 (3); Ir2-N2-Pt1, 101,5 (4); N1-Pt1-N2, 68,3 (3); N1-Pt1-C1, 101,7 (5), N1-Pt1-C2, 171,2 (6); N2-Pt1-C1, 169, 5mm (5); N2-Pt1-C2, 103,2 (6); C1-Pt1-C2, 86,6 (7).

Example 2. The synthesis of compounds 1b

At stage (3) in example 1, 4-bromoaniline was used instead of aniline to obtain [Cp(IU)*Ir(µ2NC6H4Br-4). THF solution (5 ml) [Pt2(µ-SMe)]2(18 mg, 0,031 mmol)obtained in the same way as in stage (4) in example 1 was added at room temperature to thus obtained THF solution (5 ml) of [Cp(IU)*Ir(µ2NC6H4Br-4) (51 mg, 0.051 mmol) and the mixture was stirred for 15 hours without further processing. The reaction solution was concentrated to approximately 1 ml and conducted a two-layer recrystallization when placing 5 ml of hexane into a concentrated solution for polycrystaline 1b (15 mg, 0.012 mmol, yield 24%) as black granular crystals.

1H NMR (CDCl3)

δ: 7,33, 7,02 (d, 2H each, J = 8.7 Hz, aryl), of 1.66 (s, 6H,2JPt-H= 88 Hz, Pt2), 1,24 (s, 30 H, C5Me5),

(FAB-MS)(+)

m/z = 1190 (M+-Me).

Elemental analysis

Analytically calculated for C34H44N2Br2IrPt2: C, REPRESENTED 33.47 PER; H, TO 3.64; N, 2,30.

Example 3. Synthesis of compound 1C

At stage (3) in example 1, 4-benzyloxyaniline was used instead of aniline to obtain [Cp(IU)*Ir(µ2NC6H4OCH2Ph-4)]2. THF solution (30 ml) [Pt2(µ-SMe)]2(110 mg, 0,191 mmol)obtained in the same way as in stage (4) in example 1 was added at room temperature to thus obtained THF solution (30 ml) [Cp(IU)*Ir(µ2NC6H4OCH2Ph-4)]2(410 mg, 0,391 mmol) and the mixture was stirred for 23 hours without further processing. The reaction solution was concentrated to approximately 10 ml and conducted a two-layer recrystallization when placing 25 ml of hexane into a concentrated solution to obtain compound 1C (145 mg, 0,117 mmol, 30%yield) as black granular crystals.

1H NMR (CDCl3)

δ: 7,41-of 6.96 (m, 20H, aryl), 4,88 (s, 4H, CH2Ph)of 1.80 (s, 6H,2JPt-H= 87 Hz, Pt2), to 1.42 (s, 30H, C5Me5).

(FAB-MS)(+)

m/z = 1243 (M+-Me).

Ele is entry analysis

Analytically calculated for C48H58N2About2IrPt2: C,45,23; H, 4,59; N, 2,20.

1. Iridium-platinum complex of the following formula (I):

where Cf* is selected from the group consisting of cyclopentadienyls ligand pentamethylcyclopentadienyl ligand pentamethylcyclopentadienyl ligand and pentabromoethylbenzene ligand, X represents a hydrogen atom or a group substituent selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group and organic groups that are located in the ortho-, meta - or para-position relative to the phenyl group or the combination of these provisions, and Y is selected from the group consisting of methyl group, ethyl group and through the group,
with specified organic group selected from the group consisting of alkyl groups, alkoxygroup, alkenylphenol group, alkenylacyl, alkenylphenol group, alkyloxy, aryl group, alloctype, aranceles group and aralkylated, which may have a heteroatom or a simple relationship ether, which are substituted or unsubstituted and which are C1-C30.

2. Iridium-platinum complex according to claim 1, in which Cf* is pentamethylcyclopentadienyl ligand.

3. Iridium-platinum comp is CEN according to claim 1 or 2, in which Y is a methyl group.

4. Iridium-platinum complex according to claim 1, in which the organic group selected from the group consisting of alkyl groups, alkoxygroup, aryl group, alloctype, aranceles group and aralkylated that represent1-C10.

5. Iridium-platinum complex according to claim 1, in which X represents a hydrogen atom or a group of Deputy placed in paraprotein relative to the phenyl group.

6. Iridium-platinum complex according to claim 1, in which X represents a hydrogen atom or a bromine atom or benzyloxy placed in the para-position relative to the phenyl group.

7. The method of synthesis of iridium-platinum complex, which includes stages:
(a) providing a compound of the following formula (II):

where Cf* is selected from the group consisting of cyclopentadienyls ligand pentamethylcyclopentadienyl ligand pentamethylcyclopentadienyl ligand and pentabromoethylbenzene ligand, Ph represents a phenyl group, and X represents a hydrogen atom or a group substituent selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group and organic groups that are located in the ortho-, meta - or para-position relative to the phenyl is Noah group, or a combination of these provisions;
(b) providing a compound of the following formula (III):

where Y is selected from the group consisting of methyl group, ethyl group and through the group, and Z is selected from the group consisting of methyl group, ethyl group and through the group; and (C) mixing the compounds of formula (II) and compounds of formula (III) in solution,
with specified organic group selected from the group consisting of alkyl groups, alkoxygroup, alkenylphenol group, alkenylacyl, alkenylphenol group,
alkyloxy, aryl group, alloctype, aranceles group and aralkylated, which may have a heteroatom or a simple relationship ether, which are substituted or unsubstituted and which are C1-C30.

8. The method of synthesis of iridium-platinum complex according to claim 7, in which Cf* represents pentamethylcyclopentadienyl ligand.

9. The method of synthesis of iridium-platinum complex according to claim 7 or 8, in which Y represents a methyl group.

10. The method of synthesis of iridium-platinum complex according to claim 7, in which Z represents a methyl group.



 

Same patents:

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

FIELD: agriculture.

SUBSTANCE: invention relates to a novel compound - dihydrate of iron (II) hydroascorbate riboflavinate

(II) Fe(C6H7O6)(C17H19O6N4)2H2O which is used as an additive.

EFFECT: improved development and growth of chickens.

1 cl, 1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to 1-alkenylimidazole derivatives of general formula 1 , where R is vinyl, allenyl or isopropenyl, R1 is hydrogen or methyl, E is Zn (II) or Fe(III), An is chlorine or acetate, n equals 1, 2 or 4, except compounds where R is vinyl, R1 is hydrogen, E is Zn(II), An is chlorine or acetate and n equals 2.

EFFECT: compounds have antihypoxic properties for different types of hypoxia.

5 ex, 8 tbl

FIELD: chemistry.

SUBSTANCE: enhanced catalysts useful in a range of reactions in organic synthesis, such as olefin substitution and atom or group transfer reactions, are described. The catalysts are obtained by bringing a poly-coordination complex of a group VIII metal - ruthenium, including a Schiff base polydentate ligand and one or more other ligands, into contact with an acid under such conditions that the said acid can partially break the bond between the metal and the Schiff base polydentate ligand of the said metal complex, optionally through intermediate protonation of the said Schiff base ligand.

EFFECT: improved method.

17 cl, 43 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: method involves reacting triethanol ammonium salts of o-cresoxyacetic and p-chloro-o-cresoxyacetic acid with the corresponding metal salt in alcohol or aqueous medium preferably at room temperature for 1-48 hours. The three-component complexes are extracted through solvent distillation with subsequent washing of the formed powder with ether and drying in a vacuum. The said complexes can be used as a base for making medicinal drugs.

EFFECT: design of a method of preparing complexes of o-cresoxy- and p-chloro-o-cresoxyacetic acid, triethanolamine and metals having formula n[R(o-CH3)-C6H3-OCH2COO-•N+H(CH2CH2OH)3]•MXm, where R = H, p-Cl; M = Mg, Ca, Mn, Co, Ni, Cu, Zn, Rh, Ag; X = CI, NO3, CH3COO; n = 1, 2; m = 1-3.

2 cl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis and preparation of dicyclopentadiene metathesis polymerisation catalysts. The metathesis polymerisation catalyst has the formula: , where L is a substitute selected from the group: , , . Several methods of preparing the catalyst are disclosed. The method of preparing the catalyst having formula , where , , is characterised by that, a second generation Grubbs catalyst is reacted with N,N-dialkyl-(2-vinylbenzyl)amine or 4-(2-vinylbenzyl)morpholine in an inert atmosphere at 60-85°C in the presence of a solvent, where the dialkyl- is methylethyl- or methyl(2-methoxyethyl). The method of preparing the catalyst formula , where L is a substitute selected from the group: , , , , involves reacting a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propyn-1-ol in tetrahydrofuran at boiling point of the solvent in an inert atmosphere and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The ruthenium indenylidene complex formed is extracted and then, successively in the same reactor, reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dialkylaminomethyl)styrene or 1-(2-vinylbenzyl)pyrrolidine or 4-(2-vinylbenzyl)morpholine in toluene while heating to 60-70°C in an inert atmosphere. The dialkyl- is diethyl-, methylethyl- or methyl(2-methoxyethyl)-. A dicyclopentadiene metathesis polymerisation method is disclosed, which involves polymerisation using the catalyst in paragraph 1 in molar ratio substrate: catalyst ranging from 70000:1 to 200000:1.

EFFECT: invention increases catalyst output and simplifies synthesis by reducing the number of steps, and also enables to obtain polydicyclopentadiene with good application properties.

4 cl, 1 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining physiologically active compounds, particularly to a new water-soluble complex of cis-diaminodichloroplatinum (2+) with isonicotinic acid hydrazide of formula Pt(NH3)2Cl2·2L, where L=INH is isoniaside, isonicotinic acid hydrazide. The method of preparing the complex involves reacting cis-diaminodichloroplatinum (2+) with isonicotinic acid hydrazide with subsequent extraction of the end product.

EFFECT: compound widens the range of water-soluble anti-tumour and anti-metastatic preparations; can be used in medical practice as an analogue of cisplatin on therapeutic effect, but in a more convenient form of administration due to its high solubility and low toxicity.

3 cl, 6 dwg, 1 ex

FIELD: process engineering.

SUBSTANCE: invention relates to complete methane oxidation catalysts and can be used in industries using diesel fuel. Invention covers complete methane oxidation catalysts based on strontium hexaferrites of the following composition: SrMnxFe12-xO19, where x=0, 1, 2, 6. Proposed method comprises settling catalyst components with the help of NH4HCO3 solution at constant pH equal to (7.1 to 8.0) and temperature not lower than 70°C with subsequent stages of filtration, rinsing, drying and roasting. Proposed method comprises also the stage of heat treatment at 800° to 1000° C and is realised in the presence of above described catalysts.

EFFECT: high degree of methane conversion at relatively low temperatures.

6 cl, 2 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining palladium acetate involves dissolving palladium metal in concentrated nitric acid, evaporation of the obtained solution and reaction with acetic acid, where the palladium nitrate solution after evaporation, before crystallisation of palladium (II) nitrate salt, is treated with nitrogen (II) oxide or a mixture of nitrogen (II) and (IV) oxides containing not more than 30% nitrogen (IV) oxide and acetic acid at temperature of the solution of 40-90°C with glacial acetic acid consumption of 1.5-2.5 l per kg of palladium in the solution and nitrogen (II) oxide or mixture of nitrogen (II) and (IV) oxides consumption of 1.0-2.0 m3 at normal conditions per 1 l of the initial palladium nitrate solution for 0.5-1.5 hours and the formed solution is heated in a nitrogen atmosphere at 110-140°C for not less than 2 hours with consumption of elementary nitrogen of approximately 30 m3 per 1 m3 of the formed solution.

EFFECT: obtaining palladium acetate in monophase state and avoding formation of impurities of insoluble palladium catena-poly-acetate.

3 cl, 35 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin synthesis method and more specifically to a polyethylene synthesis method. Polyethylene is a copolymer of ethylene with 1-alkenes. The invention also relates to polyethylene synthesis catalyst systems. The catalyst system is a mixture of metallocenes: hafnocene and an iron-based complex, an activating compound and a support. The invention also relates to films made from polyethylene and packets made from the said films.

EFFECT: disclosed catalyst system enables production of polyethylene with given molecular weight distribution in a single reactor.

16 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: described is a method of obtaining polymethylmethacrylate via radical polymerisation in a methylmethacrylate mass in the presence of an initiating system, one of the components of which is benzoyl peroxide. The method is distinguished by that, the second component of the initiating system used is bis-ferrocenylborate macrobicyclic tris-1,2-cyclohexanedionedioxymate of iron (II), molar ratio bis-ferrocenylborate macrobicyclic tris-1,2-cyclohexanedionedioxymate of iron (II): benzoyl peroxide equals (0.01-0.1):(0.05-1) and polymerisation is carried out at 30-60°C.

EFFECT: faster polymerisation, reduced consumption of components of the initiating system, lower polymerisation temperature, elimination of the gel effect, regulation of molecular weight of the obtained polymethylmethacrylate.

1 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: method includes carbonylation of the alcohol and/or of its reactive derivative with carbon monooxide in liquid reaction mixture carried out in carbonylation reactor. The said liquid reaction mixture contains the said alcohol and/or its reactive derivative, carbonylation catalyst, alkyl halide cocatalyst whereat the said catalyst includes at least one metal selected from rhodium or iridium coordinated with polydentate ligand whereat the said polydentate ligand has the bite angle at least 145° or forms the "hard" Rh or Ir metal-ligand complex; the said polydentate ligand includes at least two coordination groups; at least two of them independently contain P, N, As or Sb as coordination atoms. The hydrogen/carbon monooxide mole ratio is supported in the range at least 1:100 and/or carbon monooxide directed to carbonylation reactor contains at least 1 mole % of hydrogen; catalyst flexibility range is less 40°. The method is tolerable to hydrogen presence i.e. liquid side-products are formed in small amounts or are not formed at all.

EFFECT: improvement of the method of carboxylic acid and its ester obtaining.

49 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention refers to the methods of linear hydrocarbons obtaining, specifically to the method of n-alkanes obtaining. The essence of the method lies in cycloalkanes hydrogenolyse in presence of the catalysts - complexes of lanthanides chlorides crystallohydrates with aluminium alkoxyde LnCl3·3H2O·3(EtO)2AlOH in combination with i-Bu2AlH in dioxane medium at atmospheric pressure and 80°C during 6 hrs.

EFFECT: increasing of the target product yield.

1 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention concerns improved method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid, involving carbonylation of C1-C8 aliphatic alcohol and/or its reactive derivative by carbon monoxide in liquid reaction mix in carbonylation reactor. Liquid reaction mix includes indicated alcohol and/or its reactive derivative, carbonylation catalyst, alkylhalide co-catalyst and optionally water in limited concentration, the catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix. Also invention concerns application of carbolylation catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix, in carbonylation method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid.

EFFECT: enhanced carbonylation speed and selectivity.

36 cl, 6 tbl, 3 ex

FIELD: chemistry, pharmacology.

SUBSTANCE: present invention relates to method for production of indolo-pyrrolo-carbazole derivative according to formula (I) , or its pharmaceutically acceptable salt, that have antitumour activity. Invention also relates to method for production of indole compound according to formula (XII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, distinguished by conducting interreaction between compound with formula (XIII) , or its pharmaceutically acceptable salt, where R1 is definitely above, Ra and Rb are either separately C1-C7-alkyl, or together form C3-C6-alkylene group, and hydrogen gas at 1 to 5 atmospheres, in presence of hydrogenation catalyst (applied as novel catalyst as well), which consist of rhodium compound, metal compound, and optionally amine, in inert solvent at room temperature; the rhodium compound being 1 to 10% rhodium on carbon, aluminium oxide, calcium carbonate, or barium sulphate, and metal compound being nickel (II), iron (II), iron (III), cobalt (II), or cobalt (III). Method is also submitted for production of bis-indole compound by formula (VIII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, Y is hydrogen, C1-C7-alkyl, phenyl, benzyloxymethyl, or C7-C12-aralkyl, consisting in reaction of indole compound by formula (XII), or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, with ethylmagnesium chloride, or butylmagnesium chloride, or magnesium compound by formula (X) RdMgRd, where Rd is butyl, in inert solvent, followed by conducting interreaction between product obtained and maleimide compound by formula (IX) , where X is halogen, and Y as above, in inert solvent.

EFFECT: improved method for indolo-pyrrolo-carbazole production.

15 cl, 68 ex, 12 tbl

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to olefin metathesis method and comprises contacting C8-C25-unsaturated fatty acid ester or C8-C25-unsaturated fatty acid, such as methyl oleate or oleic acid, with lower olefin, preferably ethylene, in presence of metathesis catalyst to give olefin product and the same with functional ester group of functional acid group. Preferable metathesis products are 1-decene and/or methyl 9-decenoate or 9-decenoic acid, respectively. Catalyst contains organometallic complex including ruthenium or osmium atom and chelating ligand having carbenic group and electron-donor group of element selected from group VA or group VIA of Periodic table, wherein carbenic group and electron-donor group are both linked to ruthenium or osmium atom. Invention also discloses heterogeneous catalyst composition designed for metathesis method, which comprises organometallic complex and catalyst carrier. Catalyst can further be optionally supported by cross-linked polymer resin. In this latter case, organometallic complex is bound to indicated support through benzyl linkage.

EFFECT: enabled production of valuable α-olefins, increased yield of product, reduced consumption of starting materials and increased productivity of process, facilitated separation of catalyst from reaction mixture.

21 cl, 2 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: subject of invention is continuous carbonylation of long-chain aliphatic hydrocarbons to produce alcohols, acids, and other oxygen-containing products such as esters. Process comprises paraffin dehydrogenation, carbonylation, and fraction distillation-mediated end product recovery. Advantageously, mixture of paraffins containing different number of carbon atoms isolated from kerosene fraction is processed. Non-converted paraffins are recycled into dehydrogenation zone. Prior to be fed into carbonylation zone, stream is processed by selectively hydrogenating diolefins. In the carbonylation stage, homogenous catalytic system is used containing palladium/imidazole or palladium/triphenylphosphine complex, aliphatic acid (preferably formic acid), and solvent. Catalytic system further includes promoter selected from group: lithium iodide, zirconium chloride, tin chloride, and lithium bromide.

EFFECT: simplified technology, increased conversion of raw materials and selectivity in formation of desired products.

14 cl, 2 dwg, 1 tbl, 11 ex

FIELD: resin industry and organometallic synthesis.

SUBSTANCE: organometallic composition for solidifying polyisocyanate materials, which may be used for binding lignocellulose, contains complex of at least one metal ortho-ether having formula M(ROAcAc)x(OR')y, where M represents titanium, zirconium, or hafnium; ROAcAc represents moiety of acetoacetic acid ester with alcohol ROH wherein R is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 1 to 30 carbon atoms or mixture thereof; OR' represents alcohol R'OH residue wherein R' is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 7 to 30 carbon atoms or mixture thereof; each of x and y ranges between 1 and 3 and x+y=4. Mixture to be solidified contains organic isocyanate compound or mixture of organic isocyanate compounds and above-indicated organometallic composition. Lignocellulose product, containing lignocellulose material and polyisocyanate composition including above-indicated organometallic composition, is prepared by bringing lignocellulose material into contact with above polyisocyanate composition to allow lignocellulose material to be bound.

EFFECT: improved process characteristics of organometallic composition.

12 cl, 1 tbl, 7 ex

The invention relates to a method of obtaining-generatingcapacity of ethylbenzene oxidation of the latter with oxygen in the presence of a ternary catalyst system comprising a bis-acetylacetonate Nickel, electron-donor complexing compound, for example an alkali metal stearate - sodium or lithium, N-organic-2, hexamethylphosphorotriamide and phenol concentration (0,5-3,0)10-3mol/l,-generatingcapacity is used to obtain propylene oxide, the world production of which is more than 106tons per year, and 44% of production based on the use of EVP as epoxidised agent

The invention relates to a method of producing diallylmalonate containing stage (a) filing of urea and a primary alcohol in the reaction zone; (b) the filing of a catalytic complex ORGANOTIN compound, a high boiling point solvent, containing electron-donating atom is specified in the reaction zone; (C) concurrently in said reaction zone (i) the interaction part of the primary alcohol and urea in the presence of the specified ORGANOTIN compounds and the specified high boiling solvent, containing electron-donating atom, to obtain diallylmalonate, and (ii) remove diallylmalonate and ammonia from the specified reaction zone in the form of steam, and also applies to homogeneous catalyst applicable to the interaction of urea and primary alcohols to obtain diallylmalonate containing complex ORGANOTIN compounds with bidentate ligand, which forms a bidentate 1:1 and/or monodentate 1:2 adducts with R'2SnX2where X denotes Cl, R O, R COO or R COS; R'3SnX, R'2SnO, Ph3-nR SnXnor Ph4-nSnXnwhere R' denotes aqH2q-1, n= 0,1 or 2, and q = 1 - 12, and mixtures thereof

FIELD: resin industry and organometallic synthesis.

SUBSTANCE: organometallic composition for solidifying polyisocyanate materials, which may be used for binding lignocellulose, contains complex of at least one metal ortho-ether having formula M(ROAcAc)x(OR')y, where M represents titanium, zirconium, or hafnium; ROAcAc represents moiety of acetoacetic acid ester with alcohol ROH wherein R is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 1 to 30 carbon atoms or mixture thereof; OR' represents alcohol R'OH residue wherein R' is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 7 to 30 carbon atoms or mixture thereof; each of x and y ranges between 1 and 3 and x+y=4. Mixture to be solidified contains organic isocyanate compound or mixture of organic isocyanate compounds and above-indicated organometallic composition. Lignocellulose product, containing lignocellulose material and polyisocyanate composition including above-indicated organometallic composition, is prepared by bringing lignocellulose material into contact with above polyisocyanate composition to allow lignocellulose material to be bound.

EFFECT: improved process characteristics of organometallic composition.

12 cl, 1 tbl, 7 ex

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