Metal complex and supported metal complex having disiloxane as ligand, method for production therefor, and supported metal catalyst prepared by using the same

Abstract

A metal complex represented by the following Formula (1): ##STR00001##
(wherein M represents palladium or platinum; L represents a ligand selected from carbon monoxide, an olefin compound, an amine compound, a phosphine compound, an N-heterocyclic carbene compound, a nitrile compound and an isocyanide compound; n represents an integer of 0 to 2 showing the number of the ligand; and each of R.sup.1 to R.sup.4 represents an organic group). The metal complex described above can be fixed on an inorganic oxide while maintaining a skeletal structure thereof to obtain a supported metal complex, and this makes it possible to allow the supported metal complex to maintain the same catalytic activity as that of the original metal complex. Also, calcining the supported metal complex obtained in the manner described above makes it possible to obtain a supported metal catalyst which is improved in catalytic activity to a greater extent than conventional supported metal catalysts.

Claims

1. A metal complex represented by the following Formula (1): ##STR00016## wherein M represents palladium or platinum; L represents a ligand selected from an olefin compound and a phosphine compound; n represents an integer of 1 to 2 showing the number of the ligand; and each of R.sup.1 to R.sup.4 independently represents an alkoxy group having 1 to 4 carbon atoms.

2. The metal complex of claim 1, wherein L is an olefin compound selected from the group consisting of: 1,5-cycloactadiene (COD), 1,3-cyclopentadiene, 1,2,3,4,5-pentamethylcyclopentadiene, 2,5-norbornadiene, ethylene, and dibenzylideneacetone.

3. The metal complex of claim 1, wherein L is a phosphine compound selected from the group consisting of: trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, dimethylphenylphosphine, trimethylphosphite, triethylphosphite, triisopropylphosphite, tri-tert-butylphosphite, triphenylphosphite, methyldiphenylphosphite, 1,2-bis(dimethylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, and diphenylphosphinoferrocene.

4. The metal complex of claim 1, wherein L is selected from the group consisting of: 1,5-cyclooctadiene (COD), dibenzylideneacetone, trimethylphosphine, triethylphosphine, tri-tert-butylphosphine, and triphenylphosphine.

5. The metal complex of claim 1, wherein n is 1.

6. A method for producing the metal complex of claim 1, comprising reacting a metal complex L.sub.nMX.sub.2, wherein M represents palladium or platinum; L represents a ligand selected from an olefin compound and a phosphine compound; n represents an integer of 1 to 2 showing the number of the ligand; and X represents halogen or a hydroxyl group, with a disiloxane compound HOR.sup.1)(R.sup.2)SiO(R.sup.3)(R.sup.4)SiOH, wherein each of R.sup.1 to R.sup.4 independently represents an alkoxy group having 1 to 4 carbon atoms, in the presence of an alkaline metal hydride.

7. A method for the hydrosilylation reaction of olefins, comprising reacting the olefins with the metal complex compound of claim 1.

8. The method for the hydrosilylation reaction according to claim 7, wherein a central metal of the catalyst is platinum.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a drawing for comparing the C.sup.13 CPMAS NMR spectra of the metal complex (2) (Example 2) and the supported metal complex (1) (Example 4) of the present invention.

(2) FIG. 2 is a drawing for comparing the .sup.29Si CPMAS NMR spectra of the metal complex (2) (Example 2) and the supported metal complex (1) (Example 4) of the present invention.

(3) FIG. 3 is a scanning transmission electron microscope (STEM) observation drawing of the supported metal complex (1) (Example 4) of the present invention.

(4) FIG. 4 is an energy dispersive X-ray (EDX) analytical drawing of the supported metal complex (1) (Example 4) of the present invention.

(5) FIG. 5 is a scanning transmission electron microscope (STEM) observation drawing of the supported metal catalyst (3) (Example 10) of the present invention.

(6) FIG. 6 is a scanning transmission electron microscope (STEM) observation drawing of the supported metal catalyst (6) (Reference Example 3) of the conventional technology.

(7) FIG. 7 is a drawing for comparing the catalytic activities in a hydrogenation reaction of cyclooctene carried out by using the supported metal catalysts (1) and (2) (Examples 11 and 12) of the present invention, and the supported metal catalysts (4) and (5) and commercially available platinum silica catalysts (Comparative Examples 1, 2 and 4) according to the conventional technologies.

(8) FIG. 8 is a drawing for comparing the catalytic activities in a hydrogenation reaction of cyclooctene carried out by using the supported metal catalyst (3) (Example 13) of the present invention and the supported metal catalyst (6) (Comparative Example 3) according to the conventional technology.

(9) FIG. 9 is a drawing for comparing the catalytic activities (conversion rates of norbornene) in a hydrosilylation reaction of norbornene carried out by using the supported metal complex (1) and the metal complex (2) (Examples 14 and 15) according to the present invention, and platinum catalysts (chloroplatinic acid and the commercially available platinum silica catalyst) (Comparative Examples 5 and 6) according to the conventional technologies.

(10) FIG. 10 is a drawing for comparing the catalytic activities (yields of the hydrosilylation product) in a hydrosilylation reaction of norbornene carried out by using the supported metal complex (1) and the metal complex (2) (Examples 14 and 15) according to the present invention, and platinum catalysts (chloroplatinic acid and the commercially available platinum silica catalyst) (Comparative Examples 5 and 6) according to the conventional technologies.

(11) FIG. 11 is a drawing showing a change in a catalytic activity (yield of the hydrosilylation product) in the repeating several times a hydrosilylation reaction of norbornene using the supported metal complex (1) of the present invention as a catalyst.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(12) The metal complex of the present invention is represented by the following Formula (1):

(13) ##STR00006##
(wherein M represents palladium or platinum; L represents a ligand selected from carbon monoxide, an olefin compound, an amine compound, a phosphine compound, an N-heterocyclic carbene compound, a nitrile compound and an isocyanide compound; n represents an integer of 0 to 2 showing the number of the ligand; and each of R.sup.1 to R.sup.4 represents an organic group).

(14) The ligand L is not particularly limited as long as it can substantially form a coordinate bond with a central metal, and the ligand includes carbon monoxide; an olefin compound such as 1,5-cyclooctadiene (COD), 1,3-cyclopentadiene, 1,2,3,4,5-pentamethylcyclopentadiene, 2,5-norbornadiene, ethylene, dibenzylideneacetone, and the like; an amine compound such as, 2,2-bipyridyl, 1,10-phenanthroline, ethylenediamine, 1,2-bis(dimethylamino)ethane, 1,2-diphenylethylenediamine, 1,2-cyclohexanediamine, and the like; a phosphine compound such as trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, dimethylphenylphosphine, trimethylphosphite, triethylphosphite, triisopropylphosphite, tri-tert-butylphosphite, triphenylphosphite, methyldiphenylphosphite, 1,2-bis(dimethylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, diphenylphosphinoferrocene, and the like; an N-heterocyclic carbene compound such as 1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, 1,3-di-tert-butylimidazole-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidine-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-di(1-adamantyl)imidazolidine-2-ylidene, 1,3-di(1-adamantyl)imidazole-2-ylidene, 1,3-dicyclohexylimidazole-2-ylidene, and the like; a nitrile compound such as benzonitrile, acetonitrile and the like; and an isocyanide compound such as tert-butyl isocyanide, 1,1,3,3-tetramethylbutyl isocyanide and the like. Among them, 1,5-cyclooctadiene, dibenzylideneacetone, trimethylphosphine, triethylphosphine, tri-tert-butylphosphine, triphenylphosphine and the like are preferred, and 1,5-cyclooctadiene and trimethylphosphine are further preferred.

(15) Also, n represents an integer of 0 to 2 showing the number of the ligand. When the ligand is a bidentate ligand such as 1,5-cyclooctadiene, n is usually 1, and when the ligand is a monodentate ligand such as trimethylphosphine, n is usually 2.

(16) Substantially, any of the organic groups can be used independently as the organic groups R.sup.1 to R.sup.4, and from the viewpoint of making it possible to fix the metal complex on the inorganic oxide, they are preferably an alkoxy group and an amino group each having a hydrolyzability, particularly preferably an alkoxy group.

(17) The metal complex of the present invention can be synthesized, for example, by reacting a metal complex L.sub.nMX.sub.2 (wherein M represents palladium or platinum; L represents a ligand selected from carbon monoxide, an olefin compound, an amine compound, a phosphine compound, an N-heterocyclic carbene compound, a nitrile compound and an isocyanide compound; n represents an integer of 0 to 2 showing the number of the ligand; and X represents halogen or a hydroxyl group) with a disiloxane compound HO(R.sup.1)(R.sup.2)SiO(R.sup.3)(R.sup.4)SiOH (each of R.sup.1 to R.sup.4 represents an organic group) under the presence of an alkaline metal hydride.

(18) The supported metal complex of the present invention has a structure represented by the following Formula (2):

(19) ##STR00007##
(wherein M represents palladium or platinum; L represents a ligand selected from carbon monoxide, an olefin compound, an amine compound, a phosphine compound, an N-heterocyclic carbene compound, a nitrile compound and an isocyanide compound; and n represents an integer of 0 to 2 showing the number of the ligand).

(20) The inorganic oxide used in the present invention is not particularly limited, and single oxides of silicon, titanium, aluminum, zirconium, magnesium and the like, and composite oxides containing them can be used. Among them, silica as a silicon oxide, for example, amorphous silica, or composite oxides containing silica, for example, aluminosilicate, are preferably used from the viewpoints of containing numerous silanol groups as a hydroxyl group on the surface and enabling to form a strong covalent bond between the organic leaving group and the inorganic oxide. Furthermore, regular mesoporous silica or regular mesoporous metallosilicate such as MCM-41, SBA-15 and the like, zeolite such as crystalline aluminosilicate, metallosilicate, aluminophosphate, silica-aluminophosphate, and the like, porous glass, clay minerals, and the like are also preferably used from the viewpoint of enabling increase in introduced amount of the metal complex per unit weight by making use of a large surface area thereof. The inorganic oxide used in the present invention may be either compounds synthesized by known methods or commercially available products.

(21) The inorganic oxides have preferably an average pore diameter of 0.5 to 500 nm, more preferably an average pore diameter of 1 to 100 nm. Also, the inorganic oxides having a large surface area are preferred in order to combine the metal complex with the inorganic oxide at a high density, and the inorganic oxides having a specific surface area of, for example, 100 to 1500 m.sup.2/g are preferred.

(22) The supported metal complex of the present invention can be obtained, for example, by contacting an organic solvent solution of a metal complex represented by the following Formula (3) with an inorganic oxide:

(23) ##STR00008##
(wherein M represents palladium or platinum; L represents a ligand selected from carbon monoxide, an olefin compound, an amine compound, a phosphine compound, an N-heterocyclic carbene compound, a nitrile compound and an isocyanide compound; n represents an integer of 0 to 2 showing the number of the ligand; and each of R.sup.1 to R.sup.4 represents an alkoxy group having 1 to 4 carbon atoms).

(24) An inorganic oxide may be suspended in a solution prepared by dissolving the metal complex represented by Formula (3) in an organic solvent, and the suspension may be stirred at room temperature or while heating. Then, solids may be combined by filtering and this is washed and dried to thereby obtain a supported metal complex. The organic solvent includes, for example, aliphatic hydrocarbons such as pentane, hexane and the like, aromatic hydrocarbons such as toluene, xylene and the like, and ethers such as diethyl ether, dibutyl ether and the like, and they may be used alone or in a mixture.

(25) The metal complex represented by Formula (3) can be reacted with the inorganic oxide, whereby a part or all of the organic groups R.sup.1 to R.sup.4 may be eliminated, and a supported metal complex retaining an inherent skeletal structure of the metal complex can be obtained.

(26) A supported metal amount of the supported metal complex thus obtained can be determined by analysis such as ICP-OES and the like.

(27) In the supported metal complex of the present invention, the metal complex carried on the carrier may retain the skeletal structure of the metal complex before carried, and therefore the supported metal complex can maintain a catalytic action of the metal complex before being carried.

(28) As confirmed in, for example, Examples 14 and 15, described later, the supported metal complex (1) of the present invention may have a catalyst activity, as is the case with the corresponding metal complex (2) before being carried, in a hydrosilylation reaction of olefins, for example, a hydrosilylation reaction of norbornene.

(29) The supported metal catalyst of the present invention can be obtained by calcining the supported metal complex of the present invention at a temperature of 80 to 600 C. under an oxygen atmosphere. Either oxygen or air may be used for the oxygen atmosphere. A carried metal amount of the supported metal catalyst thus obtained can be determined by analysis such as ICP-OES and the like.

(30) The supported metal catalyst of the present invention can be used for various catalytic reactions in which conventional supported platinum catalysts and supported palladium catalysts are used.

(31) A method for evaluating an activity of the supported metal catalyst of the present invention is not particularly limited, and the activity thereof can be evaluated by investigating, for example, a hydrogenation reaction of olefins, which is a representative catalytic reaction with platinum metal species, for example, a hydrogenation reaction of cyclooctene.

(32) As confirmed in Examples 11 to 13 described later, the supported metal catalyst of the present invention may be improved in a catalytic activity to a large extent in a hydrogenation reaction of olefins as compared with conventional supported metal catalysts. This may be attributable to the fact that the supported metal catalyst of the present invention is formed by evenly dispersing the fine particles of the catalyst metal on a carrier, and it is apparent that a similar improvement in the catalyst activity is obtained in other catalytic reactions.

(33) The present invention shall be explained in further detail with reference to Examples and Reference Examples shown below.

EXAMPLES

Example 1

Synthesis of Metal Complex (1)

(34) 45 ml of THF solution containing HO[(tert-BuO).sub.2SiO].sub.2H (able to be synthesized by a method described in, for example, J. Beckmann, et. al., Appl. Organometal. Chem., vol. 17, p. 52 (2003), and the like) (1.02 g, 2.6 mmol) and KH (0.24 g, 6 mmol) was dropwise added to a 200 ml volume Schlenk tube containing (COD) PdBr.sub.2 (0.9 g, 2.4 mmol) and 20 ml of THF solvent, and they were reacted for 2 hours. The reaction liquid was filtered, and a matter obtained was dried under vacuum to thereby obtain the following metal complex (1) 1.1 g. The metal complex (1) was subjected to structure identification by a solution NMR spectrum.

(35) ##STR00009##

(36) Solution NMR (room temperature, solvent (C.sub.6D.sub.6))

(37) .sup.1H NMR (400 MHz); 1.26, 1.33, 2.71

Example 2

Synthesis of Metal Complex (2)

(38) A metal complex (2) 1.51 g was obtained by carrying out the same procedure as in Example 1, except that (COD) PtI.sub.2 (1.34 g, 2.4 mmol) was used. The metal complex (2) was subjected to structure identification by a solution NMR spectrum and elemental analysis (C, H analysis). Further, the NMR spectrum of the solid matter was measured for structure identification in a solid state (refer to FIGS. 1 and 2).

(39) ##STR00010##

(40) Solution NMR (room temperature, solvent (C.sub.6D.sub.6)) (1) .sup.1H NMR (400 MHz); 1.09, 1.63, 1.70, 4.66 (2) .sup.13C {.sup.1H} NMR; 29.7, 31.1, 71.7, 91.3 (3) .sup.29Si {.sup.1H} NMR; 84.9

(41) Elemental analysis (C.sub.24H.sub.48O.sub.7Si.sub.2Pt.sub.1) (1) theoretical value: C, 41.19; H, 6.91% (2) measured value: C, 41.67; H, 6.92%

Example 3

Synthesis of Metal Complex (3)

(42) A metal complex (3) 1.61 g was obtained by carrying out the same procedure as in Example 1, except that (Me.sub.3P).sub.2PtI.sub.2 (1.44 g, 2.4 mmol) was used. The metal complex (3) was subjected to structure identification by a solution NMR spectrum and elemental analysis (C, H analysis).

(43) ##STR00011##

(44) Solution NMR (room temperature, solvent (CD.sub.2Cl.sub.2)) (1) .sup.1H NMR (400 MHz); 1.31, 1.54-1.58 (2) .sup.13C {.sup.1H} NMR; 14.2-14.8, 31.2, 40.4 (3) .sup.31P {.sup.1H} NMR; 26.95

(45) Elemental analysis (C.sub.22H.sub.54P.sub.2Si.sub.2Pt.sub.1) (1) theoretical value: C, 35.52; H, 7.32% (2) measured value: C, 35.59; H, 7.15%

Example 4

Synthesis of Supported Metal Complex (1)

(46) Mesoporous silica MCM-41 (able to be synthesized by a method described in, for example, C. T. Kresge, et. al., Nature, vol. 359, p. 710 (1992) and the like) (5 g) was dried at 120 C. for 1 hour under reduced pressure. The reaction system was cooled to room temperature, and then an inside thereof was replaced with a dry nitrogen gas. The metal complex (2) (0.18 g, 0.26 mmol) and toluene (100 ml) were added thereto, and the mixture was stirred at room temperature for 24 hours. The resulting solid matter was filtered and washed three times with toluene (100 ml). Then, the solid matter was dried at room temperature for 24 hours under reduced pressure to obtain a supported metal complex (1).

(47) The solid NMR spectrum of the supported metal complex (1) was compared with that of the metal complex (2) to thereby analyze a connecting state of the metal complex (2) to the mesoporous silica carrier. The results obtained by measuring the metal complex (2) and the supported metal complex (1) by .sup.13C CPMAS NMR and .sup.29Si CPMAS NMR were shown in FIGS. 1 and 2. The peaks observed can be assigned to COD, a t-Bu group and Si as shown respectively in the drawings, and the above assignment resulted in confirming that the metal complex (2) was connected, as shown in [Chem 7], to the mesoporous silica while eliminating four t-Bu groups and that the supported metal complex (1) was obtained. Further, the supported metal complex (1) was subjected to scanning transmission electron microscope (STEM) observation and energy dispersive X-ray (EDX) analysis. The results of the STEM observation and the EDX analysis are shown in FIGS. 3 and 4. Platinum was apparently present according to the EDX analysis, but platinum particles could not be confirmed to be present by the STEM observation. The above finding resulted in confirming that platinum was carried on the mesoporous silica carrier in a state of a monoatom while retaining the original complex structure. An amount of platinum carried on the supported metal complex (1) thus obtained was determined by an ICP-OES method to result in finding that it was 1.06% by weight.

(48) ##STR00012##

Example 5

Synthesis of Supported Metal Complex (2)

(49) A supported metal complex (2) was obtained by carrying out the same procedure as in Example 4, except that the metal complex (3) (0.39 g, 0.52 mmol) was used.

(50) ##STR00013##

Example 6

Synthesis of Supported Metal Complex (3)

(51) A supported metal complex (3) was obtained by carrying out the same procedure as in Example 4, except that amorphous silica (CARiACT Q-10, manufactured by Fuji Silysia Chemical Ltd., surface area: 250 m.sup.2/g) was used as the carrier.

(52) The results obtained by measuring the supported metal complex (3) by .sup.13C CPMAS NMR and .sup.29Si CPMAS NMR were the same as in FIGS. 1 and 2, and the above matter resulted in confirming that the metal complex (2) was connected, as shown in [CHEM 9], to the amorphous silica while eliminating four t-Bu groups and that the supported metal complex (3) was obtained.

(53) ##STR00014##

Example 7

Synthesis of Supported Metal Complex (4)

(54) A supported metal complex (4) was obtained by carrying out the same procedure as in Example 4, except that the metal complex (2) (0.36 g, 0.52 mmol) was used.

Example 8

Synthesis of Supported Metal Catalyst (1)

(55) 2 g of the supported metal complex (1) was calcined at 300 C. for 3 hours in an oxygen flow to thereby obtain 1.9 g of a supported metal catalyst (1). An amount of platinum carried on the supported metal catalyst (1) thus obtained was determined by the ICP-OES method to result in finding that it was 1.04% by weight.

Example 9

Synthesis of Supported Metal Catalyst (2)

(56) 1.8 g of a supported metal catalyst (2) was obtained by carrying out the same procedure as in Example 8, except that 2 g of the supported metal complex (3) was used. An amount of platinum carried on the supported metal catalyst (2) thus obtained was determined by the ICP-OES method to be 1.03% by weight.

Example 10

Synthesis of Supported Metal Catalyst (3)

(57) 1.9 g of a supported metal catalyst (3) was obtained by carrying out the same procedure as in Example 8, except that 2 g of the supported metal complex (4) was used. The supported metal catalyst (3) was observed under STEM. The result thereof was shown in FIG. 5. Platinum was observed to be dispersed and carried relatively evenly on the mesoporous silica carrier in the form of small particles having a size of 2 to 3 nm or less. An amount of platinum carried on the supported metal catalyst (3) thus obtained was determined by the ICP-OES method to result in finding that it was 2.04% by weight.

Reference Examples

Synthesis of Supported Metal Catalysts by Conventional Technologies

Reference Example 1

Synthesis of Supported Metal Catalyst (4)

(58) 50 mL of an aqueous solution containing 0.1 g of (NH.sub.3).sub.4Pt(NO.sub.3).sub.2 was added dropwise to 5 g of mesoporous silica MCM-41 to thereby impregnate the silica with the solution, and then the mixture was dried at 60 C. for 3 hours under vacuum. The resulting powder was calcined at 300 C. for 3 hours in an oxygen flow to thereby obtain 5.1 g of a supported metal catalyst (4) containing platinum carried on the mesoporous silica. An amount of platinum carried on the supported metal catalyst (4) thus obtained was determined by the ICP-OES method to result in finding that it was 0.92% by weight.

Reference Example 2

Synthesis of Supported Metal Catalyst (5)

(59) A supported metal catalyst (5) was obtained by carrying out the same procedure as in Reference Example 1, except that the amorphous silica CARiACT Q-10 was used as the carrier. An amount of platinum carried on the supported metal catalyst (5) thus obtained was determined by the ICP-OES method to result in finding that it was about 0.91% by weight.

Reference Example 3

Synthesis of Supported Metal Catalyst (6)

(60) A supported metal catalyst (6) was obtained by carrying out the same procedure as in Reference Example 1, except that 50 mL of an aqueous solution containing 0.2 g of (NH.sub.3).sub.4Pt(NO.sub.3).sub.2 was used. An amount of platinum carried on the supported metal catalyst thus obtained was determined by the ICP-OES method to result in finding that it was about 1.68% by weight. The supported metal catalyst (6) was observed under STEM. The result thereof is shown in FIG. 6. It was confirmed that while a carried amount of platinum was small as compared with the supported metal catalyst (3), platinum was aggregated and present unevenly on the mesoporous silica carrier.

(61) [Evaluation of Catalytic Activity of Supported Metal Catalysts in Hydrogenation Reaction]

(62) The catalytic activities of the supported metal catalysts in hydrogenation reaction were evaluated using cyclooctene as olefin and hydrogen as a hydrogen source.

Example 11

(63) 20 mg of the supported metal catalyst (1) obtained in Example 8 was weighed into a

(64) Schlenk tube having a volume of 25 ml and subjected to reduction treatment at 300 C. for 1 hour in a hydrogen flow. After the Schlenk tube was cooled down to room temperature, the Schlenk tube was replaced in an inside with an argon gas and charged with 5 mL of isopropanol containing 120 L of mesitylene as a standard substance, and 2.5 mmol of cyclooctene. Then, the Schlenk tube was replaced in an inside again with a hydrogen gas, and they were reacted at room temperature under hydrogen at a pressure of 1 atmosphere while stirring. The catalytic activity was evaluated by a change with the passage of time in a yield of cyclooctane which was the product. The result thereof is shown in FIG. 7.

Example 12

(65) The catalytic activity was evaluated by carrying out the same procedure as in Example 11, except that the supported metal catalyst (2) obtained in Example 9 was used. The result thereof is shown together in FIG. 7.

Example 13

(66) The catalytic activity was evaluated by carrying out the same procedure as in Example 11, except that the supported metal catalyst (3) obtained in Example 10 was used. The result thereof is shown in FIG. 8.

Comparative Example 1

(67) The catalytic activity was evaluated by carrying out the same procedure as in Example 11, except that the supported metal catalyst (4) obtained in Reference Example 1 was used. The result thereof is shown together in FIG. 7.

Comparative Example 2

(68) The catalytic activity was evaluated by carrying out the same procedure as in Example 11, except that the supported metal catalyst (5) obtained in Reference Example 2 was used. The result thereof is shown together in FIG. 7.

Comparative Example 3

(69) The catalytic activity was evaluated by carrying out the same procedure as in Example 11, except that the supported metal catalyst (6) obtained in Reference Example 3 was used. The result thereof is shown together in FIG. 8.

Comparative Example 4

(70) The catalytic activity was evaluated by carrying out the same procedure as in Example 11, except that a commercially available 1 weight % platinum silica catalyst (manufactured by Sigma-Aldrich Corporation) was used. The result thereof is shown together in FIG. 7.

(71) [Evaluation of Catalytic Activity of Metal Complex and Supported Metal Complex in Hydrosilylation Reaction]

(72) The catalytic activities of the metal complexes and the supported metal complexes of the present invention in hydrosilylation reaction by dimethylchlorosilane using norbornene as olefin were evaluated.

(73) ##STR00015##

Example 14

(74) The supported metal complex (1) obtained in Example 5 was weighed into a Schlenk tube having a volume of 25 ml in a proportion of 0.2 mol % based on 1.2 mmol of norbornene as shown in Equation 2 and subjected to drying treatment at 80 C. for 1 hour under vacuum. After the Schlenk tube was cooled to room temperature, the Schlenk tube was replaced in an inside with an argon gas and charged with 5 ml of toluene containing 100 L of mesitylene as a standard substance, 1.2 mmol of norbornene and 2.4 mmol of dimethylchlorosilane, and then they were reacted at room temperature for 20 minutes while stirring. The catalytic activity was evaluated by a conversion rate (FIG. 9) of norbornene and a yield (FIG. 10) of the product shown in Equation 2.

Example 15

(75) The catalytic activity was evaluated by carrying out the same procedure as in Example 14, except that the metal complex (2) obtained in Example 2 was used. The results thereof are shown together in FIGS. 9 and 10.

Comparative Example 5

(76) The catalytic activity was evaluated by carrying out the same procedure as in Example 14, except that a solution obtained by dissolving chloroplatinic acid (H.sub.2PtCl.sub.6) in an isopropanol solvent was used. The results thereof are shown together in FIGS. 9 and 10.

Comparative Example 6

(77) The catalytic activity was evaluated by carrying out the same procedure as in Example 14, except that the commercially available 1 weight % platinum silica catalyst (manufactured by Sigma-Aldrich Corporation) was used and that the reaction was carried out at room temperature for 60 minutes while stirring. The results thereof are shown together in FIGS. 9 and 10.

(78) [Evaluation of Catalyst Recycling]

Example 16

(79) A recycle catalytic characteristic of the supported metal catalyst (1) was evaluated by repeating several times the same procedure as in Example 14 using the supported metal catalyst (1). The results thereof are shown in FIG. 11.

INDUSTRIAL APPLICABILITY

(80) The present invention is applicable to various technical fields using supported metal catalysts, supported metal complex catalysts and metal complex catalysts.