KR20170084792A - Hydroformylation process using catalyst composition comprising phosphite ligands - Google Patents

Abstract

The present invention relates to a method and a catalyst composition for the hydroformylation of olefinic compounds using a catalyst composition comprising a phosphorus ligand and more particularly to a process for the hydroformylation of an olefinic compound comprising a phosphite ligand having a symmetry axis in an amount of 1 to 8% (CO / H ₂ ) of an olefinic compound with carbon monoxide and hydrogen in the presence of a catalyst composition to produce an aldehyde, wherein the reaction temperature is 70 to 90 ° C, 5 to 25 bar, and the selectivity ratio of normal / iso of the produced aldehyde is less than 2.0. The present invention also relates to a method and a catalyst composition for hydroformylation of an olefinic compound.
According to the present invention, it is possible to reduce the selectivity ratio (n / i) of the produced aldehyde to n / i in the hydroformylation reaction of the olefinic compound and improve the catalytic activity and stability of the olefinic compound, There is an effect of providing a milling method and a catalyst composition.

Description

HYDROFORMYLATION PROCESS USING CATALYST COMPOSITION COMPRISING PHOSPHITE LIGANDS Technical Field [1] The present invention relates to a hydroformylation method using a catalyst composition comprising a phosphite ligand,

The present invention relates to a process for hydroformylation of an olefinic compound using a catalyst composition comprising a phosphorus ligand, and more particularly to a process for hydroformylation of an olefinic compound by hydroformylation of the olefinic compound, (N / i ratio), and is excellent in catalytic activity and stability, and relates to a catalyst composition.

Various olefins are reacted with carbon monoxide (CO) and hydrogen (H ₂ ), which are often referred to as synthesis gases, in the presence of homogeneous organometallic catalysts and ligands to form linear, normal and branched ) The hydroformylation reaction to produce an aldehyde was first discovered by Otto Roelen in Germany in 1938.

The hydroformylation reaction, which is generally known as the oxo (OXO) reaction, is an industrially important reaction in the homogeneous catalytic reaction. Various aldehydes including alcohol derivatives are produced and consumed through the above oxo process.

Various aldehydes synthesized by oxo reaction may be oxidized or hydrogenated after the condensation reaction of aldol or the like to be transformed into various acids and alcohols containing long alkyl groups. Particularly, the hydrogenated alcohols of aldehydes by this oxo reaction are called oxoalcohols. Oxoalcohols are widely used industrially, such as solvents, additives, raw materials for various plasticizers, and synthetic lubricants.

In the related art, since the value of the normal-aldehyde in the aldehyde generated by the oxo reaction was high, studies on most catalysts have been carried out to increase the proportion of the linear aldehyde derivative. Isobutyric acid, neopentyl glycol (NPG), 2,2,4-trimethyl-1,3-pentanediol (2,2,4-trimethyl-1,3-pentanediol) having an iso-aldehyde derivative as a raw material, , 4-trimethyl-1,3-pentanediol, isovaleric acid, and the like, demand for isoleic aldehyde has been increased, and studies for increasing the selectivity of the branched aldehyde derivatives have been continuing . Therefore, it is necessary to develop a catalyst having excellent catalyst stability and activity while lowering the selectivity ratio (n / i) of normal / iso of aldehyde.

KR 1150557 B1

In order to overcome the problems of the prior art, the present invention has been made to overcome the problems of the prior art by providing a catalyst composition which lowers the selectivity ratio (n / i) of the produced aldehyde to n / i ratio during the hydroformylation reaction of olefinic compounds, And a method for hydroformylation of an olefinic compound using the same.

The present invention also aims at providing the above catalyst composition.

These and other objects of the present invention can be achieved by the present invention described below.

In order to accomplish the above object, the present invention provides a process for producing olefinic compounds, a synthesis gas of carbon monoxide and hydrogen (CO / H) in the presence of a catalyst composition comprising 1 to 8% by weight of a phosphite ligand having a symmetry axis ₂ ), wherein the reaction temperature during the reaction is 70 to 90 ° C, the reaction pressure is 5 to 25 bar, and the selectivity ratio of normal / iso of the produced aldehyde is less than 2.0, A method of hydroformylation of a base compound.

The present invention also provides a catalyst composition comprising a phosphite ligand having a symmetry axis and a transition metal catalyst.

According to the present invention, it is possible to reduce the selectivity ratio (n / i) of the produced aldehyde to n / i in the hydroformylation reaction of the olefinic compound and improve the catalytic activity and stability of the olefinic compound, There is an effect of providing a milling method and a catalyst composition.

Hereinafter, the present invention will be described in detail.

The present inventors have found that when the reaction temperature and the reaction pressure are controlled within a specific range in the presence of a catalyst composition containing a specific amount of a phosphite ligand having a symmetry axis in the hydroformylation reaction of an olefin, (N / i ratio) of the catalyst of the present invention, but the catalytic activity and the stability are excellent.

The method of hydroformylation of the olefinic compound according to the present invention will be described in detail.

The method for hydroformylation of an olefinic compound comprises reacting an olefinic compound with a synthesis gas of carbon monoxide and hydrogen (CO / H) in the presence of a catalyst composition comprising 1 to 8% by weight of a phosphite ligand having a symmetry axis ₂ ) at a reaction temperature of 70 to 90 ° C., a reaction pressure of 5 to 25 bar, and a selectivity ratio of normal / iso of the produced aldehyde is less than 2.0 .

In the hydroformylation of the olefinic compound, the reaction temperature of the olefinic compound and the synthesis gas (CO / H ₂ ) in the presence of the catalyst composition may be, for example, 70 to 90 ° C or 80 to 90 ° C, The activity of the catalyst can be maintained in the hydroformylation reaction while lowering the normal / iso selectivity ratio (n / i) of the aldehyde within the range.

In the hydroformylation of the olefinic compound, the reaction pressure in the reactor may be, for example, 5 to 25 bar, 5 to 20 bar, or 5 to 15 bar, and the catalytic activity is excellent within this range.

The selectivity ratio of the normal / iso of the aldehyde produced by the hydroformylation of the olefinic compound may be less than 2.0, for example, from 1 to 1.8, or from 1 to 1.5.

The phosphite having the symmetry axis may be, for example, a phosphite in which an axis of symmetry is present based on phosphorus (P) atoms.

The phosphite ligand having the symmetry axis may be, for example, a monodentate phosphite ligand represented by the following general formula (1), wherein the activity / stability of the catalyst is lowered by lowering the n / i ratio of the aldehyde Both have excellent effects.

Two or more selected from among R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are, for example, independently an alkyl group having 1 to 15 carbon atoms, which is substituted or unsubstituted with a substituent; A cycloalkyl group or a cycloalkenyl group having 5 to 15 carbon atoms, which is substituted or unsubstituted with a substituent; A substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, and the remainder of the above-mentioned R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be hydrogen.

As another example, the _two selected from among R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; A cycloalkyl group or a cycloalkenyl group having 5 to 10 carbon atoms, which is substituted or unsubstituted with a substituent; A substituted or unsubstituted heteroalkyl group having 1 to 15 carbon atoms; Or a heterocyclic group having 4 to 15 carbon atoms which is unsubstituted or substituted with a substituent, and the remainder of the above-mentioned R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be hydrogen.

As another example, each of R ₁ and R ₃ independently represents an alkyl group having 1 to 10 carbon atoms, which is substituted or unsubstituted with a substituent; A cycloalkyl group or a cycloalkenyl group having 5 to 10 carbon atoms, which is substituted or unsubstituted with a substituent; A substituted or unsubstituted heteroalkyl group having 1 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 4 to 15 carbon atoms, and R ₂ , R ₄ and R ₅ may be hydrogen.

The substituent may be nitro (-NO ₂ ), fluorine (F), chlorine (Cl), bromine (Br) or an alkyl group having 1 to 10 carbon atoms, and the heteroalkyl group and the heterocyclic group may be N, And may contain one or more atoms selected from the group consisting of

Examples of the coordination phosphite ligand include tris (2,6-di-tert-butyl-4-methoxyphenyl) phosphite, Tris (2-tert-butyl-4-methylphenyl) phosphite, TTBMPP), tris (2,4-ditertiary- butylphenyl) phosphite Tris (2-iso-propyl-4-methylphenyl) phosphite, TDIPMPP) and tris (2-isopropyl-4-methylphenyl) phosphite, TDTBPP, (2,4-di-iso-propylphenyl) phosphite, TDIPPP). In this case, the ratio of the normal / iso selectivity of the aldehyde There is an effect of lowering the ratio (n / i ratio).

The coordination phosphite ligand may be contained in an amount of, for example, 1 to 8% by weight, 2 to 8% by weight, or 3 to 6% by weight based on the catalyst composition, and the ratio of the normal / / i ratio), the activity and stability of the catalyst are excellent, and the reaction rate is excellent.

The catalyst composition may include, for example, a transition metal catalyst represented by the following general formula (2).

The M may be at least one selected from the group consisting of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum may be one selected from the group consisting of the L ^1, L ² and L ³ are each independently for example hydrogen, carbonyl (CO), cyclooctadiene (cyclooctadiene), norbornene (norbornene), chlorine (chlorine), Triphenylphosphine (TPP), and acetylacetonato (AcAc). The x, y, and z may be, for example, independently 0 to 5, and x, y and z are not simultaneously zero.

As a specific example, the transition metal catalyst may be selected from the group consisting of cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonate dicarbonyl rhodium [Rh (AcAc) (CO) ₂ ], acetylacetonato carbonyl triphenylphosphine rhodium [Rh (CO) (TPP) ₃ ], acetylacetonitodecarbonyl iridium [Ir (AcAc) (CO) ₂ (CO) (TPP)], hydridocarbonyltri (triphenylphosphine) rhodium , And hydridocarbonyltri (triphenylphosphine) iridium [HIr (CO) (TPP) ₃ ]. In this case, the catalytic activity is excellent.

The transition metal catalyst may be contained in an amount of, for example, 1 to 1,000 ppm, 10 to 800 ppm, or 50 to 500 ppm based on the catalyst composition, and the hydroformylation reaction rate is excellent within this range.

The catalyst composition may be one or more selected from the group consisting of propane aldehyde, butylaldehyde, pentylaldehyde, valeraldehyde, acetone, methylethylketone, methylisobutylketone, acetophenone, cyclohexanone, ethanol, pentanol, , At least one solvent selected from the group consisting of toluene, xylene, ortho-dichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride and heptane. In this case, .

The catalyst composition may have a catalytic activity of 300% or more, 500% or 500% to 1,000% based on the activity of the catalyst composition containing triphenylphosphine compound, .

The catalyst composition may be used in a catalyst composition having a catalyst stability of at least 100, for example, at least 90 ° C, at 90-150 ° C, or at a deactivation temperature of 100-120 ° C for 15 hours, based on the gas consumption of the catalyst composition comprising the triphenylphosphine compound %, 100 to 500%, or 100 to 350%. Within this range, there is an effect of excellent catalyst stability.

The olefin-based compound may be, for example, a compound represented by the following formula (3).

R ₆ and R ₇ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), trifluoromethyl (-CF ₃ ) It has a substituent may be an aryl date having 6 to 20 carbon atoms, the substituent of the aryl group for example a nitro (-NO _2), fluorine (F), chlorine (Cl), bromine (Br), methyl, ethyl, propyl or butyl Lt; / RTI >

As a specific example, the olefin compound may be at least one member selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene and styrene.

The method of hydroformylation of the olefinic compound may be represented by the following reaction formula 1, for example.

[Reaction Scheme 1]

As a specific example, a transition metal catalyst represented by Formula 2 and an uni-coordinated phosphite ligand represented by Formula 1 are dissolved in the solvent to prepare a mixed solution of a transition metal catalyst and a ligand, (CO / H ₂ ) are introduced into a conventional reactor, and the reaction is carried out under elevated temperature and pressure while stirring to produce an aldehyde.

The mixing ratio of carbon monoxide and hydrogen in the synthesis gas (CO / H ₂ ) may be 5:95 to 70:30, 40:60 to 60:40, or 45:55 to 55:45 based on the molar amount, The gas used for the reaction is not accumulated in the reactor, and the reactivity of the catalyst is excellent.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory only and are not to be taken by way of illustration in the practice of the practice of this invention. And it is to be understood that such variations and modifications are within the scope of the appended claims.

[Example]

Control Example

0.12 g (0.3 mmol) of triphenylphosphine (TPP) and 0.12 g (0.3 mmol) of acetylacetonato carbonyl triphenylphosphine Rh (AcAc) (CO) The solution was dissolved in a valeraldehyde solvent so that the total solution became 100 g (Rh 250 ppm, TTP 6 wt%) and then charged into a 600 ml autoclave reactor. Propylene and a synthesis gas (CO / H ₂ ) were injected into the reaction solution, and the pressure in the reactor was maintained at the reaction pressure shown in Table 1, and the reaction was carried out for 1 hour while stirring at the reaction temperature shown in Table 1 below.

Examples 1 to 4 and Comparative Examples 1 to 5

In the above control examples, the phosphite compounds and phosphine compounds described in the following Table 1 were added in place of the triphenylphosphine compound (triphenylphosphine (TPP) as a ligand in the stated weight percentages and reacted at the reaction pressure and the reaction temperature The same procedure was followed as in the above-mentioned control example.

How to measure

* N / i ratio of aldehyde (n / i ratio): The amount of produced normal-butyraldehyde was divided by the amount of iso-butyraldehyde, and each aldehyde Was determined by gas chromatography (GC) analysis after the reaction.

division The catalyst (Rh) Ligand Ligand content (% by weight) Reaction temperature (캜) Reaction pressure (bar) n / i ratio Control Example ROPAC TPP 6 90 8 9.1 80 6.7 <80 - Example 1 ROPAC TTBMPP 3 90 18 1.09 80 1.13 70 1.35 60 1.57 50 1.80 <50 - Example 2 ROPAC TTBMPP 6 90 8 1.24 80 1.43 70 1.77 60 2.15 50 2.25 <50 - Example 3 ROPAC TDTBPP 3 90 18 1.16 80 1.30 70 1.47 60 1.69 <60 - Example 4 ROPAC TDTBPP 6 90 8 1.39 80 1.61 70 1.88 60 2.16 <60 - Comparative Example 1 ROPAC CHDP 3 90 8 1.92 80 2.31 75 2.71 <75 - Comparative Example 2 ROPAC A 3 90 18 1.61 80 2.14 70 2.55 Comparative Example 3 ROPAC A 6 90 8 2.02 80 2.66 70 2.92 Comparative Example 4 ROPAC B 3 90 18 1.81 80 2.32 70 2.51 Comparative Example 5 ROPAC B 6 90 8 1.97 80 2.55 70 3.02

TTBMPP: Tris (2-tert-butyl-4-methylphenyl) phosphite

* TDTBPP: Tris (2,4-di-tert-butylphenyl) phosphite (Tris (2,4-

* CHDP: Cyclohexyldiphenylphosphine

* A:

* B:

As shown in Table 1, in Examples 1 to 4 according to the present invention, the selection ratio of the normal / iso of aldehyde was lower than that of the control, and the selectivity of iso-butylaldehyde was excellent, The selectivity ratio of the normal / iso of the aldehyde of less than 2.0 at the reaction temperature of &lt; RTI ID = 0.0 &gt; On the other hand, the reaction did not proceed at a reaction temperature of less than 50 ° C in each of Examples 1 and 2, and at a reaction temperature of less than 60 ° C in Examples 3 and 4, respectively.

On the other hand, in the case of the control using the phosphine ligand and the comparative example 1, the selection ratio of the normal / iso of the aldehyde was very high, and the reaction did not proceed at temperatures lower than 80 ° C and 75 ° C, In the case of Comparative Examples 2 to 5 using A and B, it was confirmed that the selection ratio of normal / iso of aldehyde was very high at a temperature of 70 to 90 ° C.

[Additional Test Example]

The catalytic activity and the catalyst stability of the catalyst compositions prepared in the Control Examples, Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the following methods and are shown in Table 2.

How to measure

* Catalytic activity (%): The total amount of normal and isobutylaldehyde produced by the reaction (reaction pressure 8 bar, reaction temperature 90 ° C) according to the control example was 100% based on each Example and Comparative Example The total amount of n-isobutyl aldehyde produced by the reaction was calculated as a percentage by the following equation (1).

[Equation 1]

Catalytic activity = total amount of normal and isobutyl aldehyde in the examples or comparative examples / total amount of normal and isobutyl aldehydes in the control examples X 100

* Normal stability (%): The amount of propylene gas consumed in the reaction was measured according to the control example (reaction pressure: 8 bar, reaction temperature: 90 ° C) The catalyst solution was inactivated at the deactivation temperature shown in the following Table 1 for 15 hours and subjected to the hydroformylation reaction (reaction pressure: 8 bar, reaction temperature: 90 ° C) in the same manner. Thereafter, the propylene gas consumption And the consumption of propylene gas before inactivation of the control example and the consumption of propylene gas after deactivation for 15 hours in the control example, the example or the comparative example were calculated as a percentage by the following formula (2) .

&Quot; (2) &quot;

Catalyst Stability = propylene gas consumption of the reaction after deactivation for 15 hours in the Control, Control or Comparative Example / consumption of propylene gas before inactivation of the Control Example X 100

division The catalyst (Rh) Ligand Ligand content (% by weight) Catalyst activity (%) Deactivation temperature (캜) Catalyst stability (%) Control Example ROPAC TPP 6 100 120 42 Example 1 ROPAC TTBMPP 3 680 120 107 100 291 Example 2 ROPAC TTBMPP 6 504 120 127 100 330 Example 3 ROPAC TDTBPP 3 900 120 178 100 105 Example 4 ROPAC TDTBPP 6 750 120 212 100 260 Comparative Example 1 ROPAC CHDP 3 115 120 61 Comparative Example 2 ROPAC A 3 580 120 4 100 55 Comparative Example 3 ROPAC A 6 620 120 5 100 18 Comparative Example 4 ROPAC B 3 680 120 4 100 63 Comparative Example 5 ROPAC B 6 730 120 7 100 22

As shown in Table 2, it was confirmed that the catalyst compositions of Examples 1 and 4 prepared according to the present invention had significantly higher catalytic activity and higher stability even after deactivation, as compared with the control examples. Further, by controlling the deactivation temperature as described above, it was confirmed that the deactivation temperature of the catalyst composition affects the catalyst stability.

On the other hand, in the case of Comparative Example 1 using a phosphine compound as a ligand and Comparative Examples 2 to 5 using a cyclic phosphite ligand A and B, it was confirmed that the catalyst stability after the deactivation sharply decreased.

From this, the present inventors have found that when the reaction temperature and the reaction pressure are controlled within a specific range in the presence of a catalyst composition containing a specific amount of a phosphite ligand having a symmetry axis in the hydroformylation reaction of an olefin, The amount of the ligand of the aldehyde of the present invention can be used in an appropriate amount, which is preferable from the viewpoint of cost and commerciality. From this, while maintaining the activity and stability of the catalyst, It was confirmed that the selectivity ratio (n / i ratio)

Claims (11)

Reacting an olefinic compound with a synthesis gas (CO / H ₂ ) of carbon monoxide and hydrogen in the presence of a catalyst composition comprising 1 to 8 wt% of a phosphite ligand having a symmetry axis to produce an aldehyde Lt; / RTI &gt;
In the reaction, the reaction temperature is 70 to 90 ° C, the reaction pressure is 5 to 25 bar,
Wherein the selectivity ratio of normal / iso of the produced aldehyde is less than 2.0. The method according to claim 1,
Wherein the phosphite ligand is a mono-coordinated phosphite ligand represented by the following formula (1).
[Chemical Formula 1]

(Wherein at least two selected from among R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A cycloalkyl group or a cycloalkenyl group having 1 to 15 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen and the substituent is nitro (-NO ₂ ), fluorine (F), chlorine (Cl), bromine (Br) To 10 carbon atoms, and said heteroalkyl group and heterocyclic group contain at least one atom selected from the group consisting of N, O and S) The method according to claim 1,
Wherein the catalyst composition comprises a transition metal catalyst represented by the following formula (2).
(2)

(M is at least one element selected from the group consisting of Co, Rh, Ir, Ru, Fe, Ni, Pd, Pt, Lt; RTI ID = 0.0 &gt;
Wherein L ¹ , L ² and L ³ are each independently selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) Acetylacetonato, AcAc, and the like.
X, y and z are each independently 0 to 5, and x, y and z are not 0 at the same time) The method of claim 3,
The transition metal catalyst may be selected from the group consisting of cobalt carbonyl [Co ₂ (CO) ₈ ], acetylacetonateddicarbonyl rhodium [Rh (AcAc) (CO) ₂ ], acetylacetonato carbonyl triphenylphosphinodiode [Rh (CO) (TPP) ₃ ], acetylacetonate dicarbonyl iridium [Ir (AcAc) (CO) ₂ ], and hydridocarbonyltri (triphenylphosphine) rhodium Wherein the at least one compound is at least one member selected from the group consisting of hydridocarbonyl tri (triphenylphosphine) iridium [HIr (CO) (TPP) ₃ ]. The method of claim 3,
Wherein the content of the transition metal catalyst is 1 to 1,000 ppm based on the catalyst composition. The method according to claim 1,
The catalyst composition may be selected from the group consisting of propane aldehyde, butylaldehyde, pentylaldehyde, valeraldehyde, acetone, methylethylketone, methylisobutylketone, acetophenone, cyclohexanone, ethanol, pentanol, , At least one solvent selected from the group consisting of ortho-dichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride and heptane. The method according to claim 1,
Wherein the olefinic compound is a compound represented by the following formula (3).
(3)

Wherein R ₆ and R ₇ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), trifluoromethyl (-CF ₃ ) Gt; is an aryl group having 6 to 20 carbon atoms,
The substituent of the aryl group is nitro (-NO ₂ ), fluorine (F), chlorine (Cl), bromine (Br), methyl, ethyl, 8. The method of claim 7,
Wherein the olefinic compound is at least one member selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene and styrene. The method according to claim 1,
Wherein the mixing ratio of carbon monoxide and hydrogen in the synthesis gas (CO / H ₂ ) is 5:95 to 70:30 based on the molar ratio. The method according to claim 1,
Wherein the catalyst composition has a catalyst stability of at least 100% based on the gas consumption of the catalyst composition comprising the triphenylphosphine compound after deactivation at a deactivation temperature of 90 DEG C or higher for 15 hours . A coordination phosphite ligand represented by the following formula (1) and a transition metal catalyst represented by the following formula (2)
Wherein said mono-coordinated phosphite ligand is comprised between 1 and 10 wt%.
[Chemical Formula 1]

(Wherein at least two selected from among R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A cycloalkyl group or a cycloalkenyl group having 1 to 15 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen and the substituent is nitro (-NO ₂ ), fluorine (F), chlorine (Cl), bromine (Br) To 10 carbon atoms, and said heteroalkyl group and heterocyclic group contain at least one atom selected from the group consisting of N, O and S)
(2)

(M is at least one element selected from the group consisting of Co, Rh, Ir, Ru, Fe, Ni, Pd, Pt, Lt; RTI ID = 0.0 &gt;
Wherein L ¹ , L ² and L ³ are each independently selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) Acetylacetonato, AcAc, and the like.
X, y and z are each independently 0 to 5, and x, y and z are not 0 at the same time)