JPS5921880B2 - New palladium complex compound and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel palladium complex compound.

Specifically, the present invention relates to a novel palladium complex compound coordinated with an olefin. Olefin complex compounds of transition metals are known in the field of organometallic chemistry to be useful as catalysts for various reactions such as polymerization and addition of olefins, acetylene, etc. In particular, olefin complex compounds of o-valent transition metals are considered to be highly useful.
Nickel has been widely studied. However, research on O-valent olefin complex compounds of palladium and platinum has hardly progressed. Recently, Stone et al. isolated a complex compound in which palladium and platinum are coordinated with 1,5-cyclooctadiene, ethylene, and norbornene [Chemical Garbage 5, Unication (Chem, C0mm dish, p. 3) (
1975) and p. 449 (1975) and Journal of Chemical Society Dalton Transactions (J.Chem.SOc.Dalt
On) p. 271 (1977)], but these are all complex compounds in which the same olefin atom is coordinated.
Such palladium complex compounds were extremely unstable and could not be used industrially.

The present inventors have previously succeeded in synthesizing tris(dibenzylideneacetone)dipalladium(0), which is a stable olefin complex compound of O-valent palladium [Chem.
Year 0 and Journal of Organometallic Chemistry (J.OrganOmetal.Chem.) 65
vol. 253 (1974)], and as a result of further intensive research based on this, we have arrived at the present invention.

That is, the present invention relates to a palladium complex compound in which two or more types of olefins are coordinated to O-valent palladium, and a method for producing the same,
The gist is general formula (1). Pd(L)m(L')n・・・・・・・・・・・・(1
) (wherein L is an electron-donating olefin selected from the group consisting of cycloolefins and cycloalkadienes, L
' represents an electron-accepting olefin selected from the group consisting of maleic anhydride, fumaronitrile and tetracyanoethylene; m and n represent 1 or 2;

) and tris(dibenzylideneacetone)dipalladium(0)
and an electron-donating olefin selected from the group consisting of cycloolefins and cycloalkadienes, and an electron-accepting olefin selected from the group consisting of maleic anhydride, fumaronitrile, and tetracyanoethylene. General formula (1): Pd(L)m(L/)
n... (1) (wherein, L represents the above-mentioned electron-donating olefin, L'' represents the above-mentioned electron-accepting olefin, and m and n represent 1 or 2.

), and bis(
The general formula (fumaronitrile) is characterized by reacting palladium with an electron-donating olefin selected from the group consisting of cycloolefins and cycloalkadienes.
):Pd(L)m(L″)n・・・・・・・・・・・・
() (wherein L represents the above electron-donating olefin, L' represents fumaronitrile, and m and n represent 1 or 2.

) is a method for producing a palladium complex compound represented by

The present invention will be explained in detail below.

In the palladium complex compound according to the present invention, there are many types of olefins that coordinate with palladium.
Generally, when olefins are divided into electron-donating olefins and electron-accepting olefins, palladium complex compounds have the general formula (1) Pd(L)n1(L')n...
...(1) (wherein L represents an electron-donating olefin, L' represents an electron-accepting olefin, and m and n represent 1 or 2.

).

Electron-donating olefins are olefins that usually donate electrons to palladium, such as alkenes such as ethylene, propylene, butene, hexene, and octene, cyclobenzene, cyclohexene, cyclooctene,
Cycloolefins such as cyclododecene and norbornene, alkadienes such as butadiene, hexadiene, octadiene, and isoprene; cycloalkadienes such as cyclohexadiene, cyclooctadiene, norbornadiene, and synclopentadiene; octatriene, dodecatriene, cyclooctatriene, and cyclododeca Examples include polyenes such as triene, cyclooctatetraene, cyclododecatetraene, and fulvalene, but in the present invention, an electron-donating olefin selected from the group consisting of cycloolefins and cycloalkadienes is used.

Electron-accepting olefins are olefins that usually accept electrons from palladium, such as maleic anhydride, dimethyl maleate, dimethyl fumarate, diethyl fumarate, methyl acrylate, methyl vinyl ketone, acrylonitrile, maleonitrile, fumaronitrile. Examples include olefins substituted with electron-withdrawing substituents such as , tetracyanoethylene, tetrafluoroethylene, benzoquinone, chloranil, and naphthoquinone; however, in the present invention, the group consisting of maleic anhydride, fumaronitrile, and tetracyanoethylene An electron-accepting olefin selected from

In the case of mono-olefins, these olefins coordinate palladium with one π-electron system, but in the case of polyenes such as dienes, depending on their structure and manufacturing conditions, two π-electron systems coordinate with palladium.
Palladium may be coordinated with more than one pi-electron system.
The compound according to the present invention can be produced, for example, by the following method.

Specifically, examples include a method of reacting tris(dibenzylideneacetone)dipalladium or tris(tribenzylideneacetylacetone)tripalladium and two or more types of olefins, and a method of reacting bis(fumaronitrile)palladium and olefins. The reaction of tris(dibenzylideneacetone)dipalladium or tris(tribenzylideneacetylacetone)tripalladium and two or more olefins is usually carried out in an inert solvent.

Examples of such inert solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, halogenated hydrocarbons such as dichloromethane, chloroform, hydrogen tetrachloride, and trichloroethane, and nitrites such as acetonitrile and propionitrile. Although preferably used, in some cases, alkanes such as pentane, hexane, and cyclohexane, aromatic compounds such as benzene and toluene, or diethyl ether,
Ether compounds such as dibutyl ether can be used. Furthermore, depending on the type of complex compound, nonaqueous solvents such as dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, etc. can also be used. moreover,
It is also possible to use the raw material olefin as a solvent. As the olefin, those containing one or more types of electron-donating olefins (L) and one or more types of electron-accepting olefins (L'') are usually used.

The amount of olefin used is usually in excess of palladium in order to allow the reaction to proceed in a short time.

The preferred amount varies depending on the type of target complex compound or olefin, but in the case of electron-donating olefin, it is 2 to 200% per mole of tris(dibenzylideneacetone)dipalladium or tris(tribenzylideneacetylacetone)tripalladium. The amount is selected to be about mol, more preferably about 10 to 50 mol. Further, in the case of an electron-accepting olefin, the amount is generally about 2 to 100 moles, more preferably about 2 to 25 moles.

The amount of the olefin to be used is not necessarily limited, and is appropriately selected so that the reaction can be carried out in a short time and the separation operation after the reaction can be simplified. Although the reaction temperature is not necessarily limited, it is usually 0 to 100°C,
Preferably, a range of about 10 to 50°C is selected.

Since employing an unnecessarily high temperature may cause decomposition of some complex compounds, a temperature around room temperature is usually suitably employed. Reaction time is a factor that correlates with various conditions such as reaction temperature, but it is usually 0.5 for reactions at room temperature.
~2 hours or more is sufficient. The reaction is preferably carried out under an inert gas atmosphere.

Examples of the inert gas include helium, argon, nitrogen, and the like. After the reaction, leave it alone or concentrate it if necessary.
It can be isolated and purified by various methods such as cooling or adding anti-solvents.

Furthermore, the reaction between bis(fumaronitrile)palladium and olefin is usually carried out in the same inert solvent as described above.

As the olefin, electron-donating olefin (L) is usually used.
Use.

The amount of olefin used is in excess relative to bis(fumaronitrile)palladium.

Preferably, the amount of olefin is about 1 to 100 mol, preferably about 5 to 50 mol, per 1 mol of bis(fumaronitrile)palladium. The reaction conditions and post-treatment method were as follows: Tris(dibenzylideneacetone)
It may be the same as the case where palladium is used as a raw material. Note that the raw material bis(fumaronitrile)palladium can be easily produced by reacting tris(dibenzylideneacetone)dipalladium and fumaronitrile in an inert solvent, as shown in the reference examples.

According to this method, a complex compound in which one component of olefin is fumaronitrile can be easily produced.

The palladium complex compound according to the present invention is novel and is useful as a catalyst or an intermediate for the synthesis of various compounds.

Moreover, according to the production method of the present invention, the compound of the present invention can be produced with very simple operations and under mild reaction conditions. EXAMPLES The present invention will be explained in more detail with reference to examples and reference examples below, but the present invention is not limited in any way by the following examples unless the gist of the invention is exceeded. Note that all of the following reactions were performed under an argon atmosphere.

Further, the infrared absorption (IR) spectrum was measured using a KBr pellet, and the NMR spectrum was measured at 60 MHz. The yield was expressed in mol%, and the elemental analysis was expressed in weight%. Example 1 (1,5-cyclooctadiene)(maleic anhydride)palladiumtris(dibenzylideneacetone)dipalladium [hereinafter abbreviated as (Dba)3Pd2] (800η;0.
873mm01) and maleic anhydride (574η; 5
．． 86mm01), 1,5-cyclooctadiene (1530η; 14.15mm01) in acetone (
Approximately 10 ml of the solution was added with stirring at room temperature.

The deep reddish-purple suspension gradually turned into a yellow-green solution. After stirring at room temperature for 0.5 hour, the mixture was filtered to remove a trace amount of metallic palladium. The resulting yellow solution was concentrated under reduced pressure to about 1 ml, a large excess of ether and n-hexane were added, and the mixture was left in a refrigerator overnight. When filtered, a deep yellow (1,5-cyclooctadiene) (maleic anhydride) was found.
A columnar crystal of palladium 176η (yield 32%) was obtained.
M. p. lO2~105℃ (Dec.) NMR spectrum (acetone D6) τ value; 4.16 (Sl4, 1・5-
cyclooctadiene olefin proton), 5.60
(S.2, maleic anhydride), 7.52 (Brl, 8,
1.5-cyclooctadiene) IR spectrum; 180
2.1731C! ! L-1 (νCO) elemental analysis as Cl2Hl4O3Pd Example 2 (norbornadiene) (maleic anhydride) palladium (
Dba)3Pd2(206η;0.225mm01),
A reaction was carried out in the same manner as in Example 1 using maleic anhydride (256 η; 2.61 mm 01), norbonadiene (615 η; 6.68 mm 01) and acetone (10 m 0 ).

As a result, (nobornadiene) (maleic anhydride) palladium was obtained as a pale yellow powder from 97.4 to 97.4 (yield 73%).
was gotten. M. p. l3O~132℃ (Dec.) IR spectrum; 1815, 1750CTIL-1 (ν
CO) Elemental analysis as CllHlOO3Pd Example 3 Pis(synchropentadiene)(maleic anhydride)palladium(Dba)3Pd2 (170W; 0.185mm
01) and maleic anhydride (71.7 w; 0.731
mm01), synchropentadiene (928
Immediately; 7.02mm01) of dichloromethane (10wL1
) solution was added at room temperature.

After stirring at room temperature for 0.5 hour, the deep reddish-purple suspension turned into a yellow-green solution. After filtering this solution, approximately 37! Concentrate under reduced pressure until it becomes Ll, and add ethyl ether (approximately 3ml) to this.
) was added gradually.

Upon filtration, 80.4 w (yield: 47%) of bis(synchropentadiene)(maleic anhydride) palladium in the form of white needles was obtained. M. p. ll4~117℃ (De
c. ) IR spectrum: 1814, 1758CWL-1 (νC
O) Elemental analysis Example 4 as C24H26O3Pd Bis(norbornene)(maleic anhydride)palladium (
Dba)3Pd2 (150η; 0.163mm01) and maleic anhydride (29.08η:0.297mm0
1), norbornene (754 w; 8.01 m
m01) in acetone (5d) was added at room temperature.

The mixture was stirred at room temperature for 0.5 hour, and the resulting yellow-green solution was filtered. The filtrate was concentrated under reduced pressure until the volume was about 1 ml, and norbornene (about 300η) and a large excess of ether were added.
It was kept at 15°C for several days. When filtered, a pale yellow bis(
norbornene) (maleic anhydride) palladium is 37,
17f9 (yield 29%) was obtained. IR spectrum; 1
809, 1745cTn-1 (νCO) NMR spectrum (CDCl3) τ value; 5.25 (Sl4, olefin proton of norbornene), 5.38 (Sl2, maleic anhydride), 6.92 (Sl4, bridgehead proton of norbornene) , 8.0 to 9.5 (Complexm, norbornene) Example 5 Bis(maleic anhydride) (norbornene) Palladium (Dba) 3Pd2 (150 instant; 0.
164 mm 01) and maleic anhydride (262 w; 2
．． 67mm01), norbornene (154m
A solution of f7; 164 mm 01) in acetone (5 m 0) was added at room temperature.

After stirring at room temperature for 0.5 hour, the deep reddish-purple suspension turned into a yellow-green solution. This solution was filtered, concentrated to about 1 ml, and a large excess of ethyl ether was added. Upon filtration, 48.0 w (yield: 41%) of bis(maleic anhydride)(norbornene)palladium was obtained in the form of silver-gray needle-like crystals. M. p. l32-134℃ (Dec.) R spectrum: 1825, 1765CTrL-1 (νC
O) Elemental analysis Example of use as Cl5Hl4O6Pd 1 Addition reaction between olefin and acetylene was carried out using bis(maleic anhydride)(norbornene)palladium as a catalyst.

The reaction formula is as follows. 94.2 m' of bis(maleic anhydride) (norbornene) palladium (0) was placed in a 30 m1 eggplant-shaped flask equipped with a dropping load with a capacity of 30 m1.
(0.24 mn101) was added.

After creating an argon atmosphere in the system, 1.827 (26.0 mm01) of 1-benzene and 3 ml of chloroform were added under a nitrogen stream, and the mixture was heated to 40° C. in an oil bath. Next, dimethyl acetylenedicarboxylate (hereinafter abbreviated as DMAD) 0
．． A DMAD-chloroform solution in which 58f (4.10 mm01) was dissolved in 15 ml of chloroform was added dropwise very slowly over 6 to 7 hours using a dropping load. After the dropwise addition was completed, the mixture was stirred at 40° C. for one and a half days. After stirring, the reaction solution was concentrated and subjected to silica gel column chromatography (15 t of silica gel; developing solution: ether/
The mixture was separated and purified using n-hexane (3/2) to obtain a substituted maleic acid ester. Yield 803.2W9 Yield 76% The product was identified by IR and 1H-NMR.

Experiments using 1-hexene, 1-heptene, and 1-octene as olefin components were conducted in the same manner, and Table 1
summarized the results. Further, spectral data of the product is shown in Table 2.

Example 6 In Example 4, the molar ratio of norbornene/palladium was set to 7, the molar ratio of maleic anhydride/palladium was set to 5, and no norbornene was added after concentration under reduced pressure. Palladium (maleic anhydride) and bis(maleic anhydride) (
A mixture of palladium (norbornene) was obtained.

Example 7 Bis(maleic anhydride)(cyclobenzene)palladium(Dba)3Pd2(182~;0.199mm01)
Maleic anhydride (184ヮ:1.88mm01) and cyclobenzene (0.5ml) in synchromethane (4m
Using 0 solution and operating in the same manner as in Example 5, 72η (yield 49%) of silver gray columnar crystals of bis(maleic anhydride)(cyclobenzene)palladium were obtained.

M. p. 9O~9'C(Dec.) IR spectrum; 1825, 1808, CTIL-1 (νCO) Elemental analysis Example 8 as Cl3Hl2O6Pd Bis(maleic anhydride)(cyclohexene)palladium(Dba)3Pd2(150η:0.164mm01 )
and maleic anhydride (91.7 w: 0.935 mm0
Cyclohexene (9 ml) and dichloromethane (6 ml) were added to the mixture of 1), and the mixture was stirred at room temperature for 1 hour.

The resulting dark reddish brown solution was diluted with cyclohexene (5
It was filtered into m0, concentrated to about 10ml and kept at -15°C. When filtered, silver plate-like crystals of bis(maleic anhydride)(cyclohexene)palladium were found to be 48771f(
Yield: 38%). M. p. 62-64℃ (Dec.
．． ) IR spectrum; 1825, 1765 cm-1 (νCO
) Reference example 1 Bis(fumaronitrile) palladium (Dba)3Pd2 (413~;0.451mm01)
and fumaronitrile (179W9; 2.296mm0
A solution of 1) in acetone (10 ml) was stirred at room temperature for 2 hours.

The color of the solution changed from deep reddish-purple to light yellow. By filtration, a pale yellow bis(fumaronitrile) palladium powder of 149~ (yield 63%) was obtained. This substance is sparingly soluble in most organic solvents except acetonitrile. M. p.
83-85°C (Dec.) IR spectrum; 2235, 2230 cm-1 (νCN
) Elemental analysis as C8H4N4Pd Example 9 Bis(norbornene)(fumaronitrile)palladium (
1) (Dba)3Pd2 (150η; 0.164mm
01) and fumaronitrile (84.27nf7; 1.
Norbornene (534W;
Add 5.67mm01) of acetone (5m0 solution,
*After stirring for 0.5 hour at room temperature, the deep reddish-purple suspension changed to a yellow-green solution.

After filtration, the filtrate was concentrated under reduced pressure to about 2 ml.
A small amount of ethyl ether was added dropwise until a small amount of crystals precipitated, and the mixture was left in the refrigerator for 24 hours. 62.5 w (yield: 61%) of bis(norbornene)(fumaronitrile)palladium was obtained as pale yellow columnar crystals. M. p. 86~
87°C (Dec.) IR spectrum; 2230 cm-1 (νCN) Elemental analysis as Cl8H22N2Pd (2) Bis(fumaronitrile)palladium (35.5~; 0.135 mm01) synthesized in Reference Example 1 in dichloromethane (5 m0 solution) , norbornene (419W9;4
．． A solution of 46 mm01) in dichloromethane (5 ml) was added, immediately turning into a dark black solution.

After stirring for 0.5 hours, a trace amount of metallic palladium was filtered off to obtain a pale yellow solution.

It was concentrated under reduced pressure and ethyl ether was added. By filtration, 26~ (yield 52%) of bis(norbornene)(fumaronitrile)palladium was obtained as pale yellow columnar crystals.
The physical property values were the same as in case (1). Usage Example 2 A co-trimerization reaction between olefin and acetylene was carried out using bis(norbornene)(fumaronitrile)palladium as a catalyst.

The reaction formula is as follows. (fumaronitrile)bis(norbornene)palladium (84.0~,0
．． After adding a solution of 225mm01) in chloroform (5ml), add 1 hexene (2.8ml1122.6mm01).
) and dimethyl acetylenedicarboxylate (0.28ml
2.28 mn101)3 was added in this order and the tube was sealed under nitrogen.

The reaction tube was placed in an oil bath maintained at 40°C, and the reaction was allowed to proceed for 2 days with magnetic stirring. After the reaction is completed, the package is opened, a small amount of precipitate is filtered, the resulting solution is concentrated, and the residue is subjected to silica gel column chromatography (Talc 17734 is added to
0y), a mixed solvent of ether/hexane=3/8>2 was separated as a developing solution. As a result, 7 of Rf=0.58
・8-bis(methoxycarbonyl)tetradeca-4.7
-diene (2-a) is 277Tf9, Rf-0.23 5-butyl-1,2,3,4-tetrakiz(methoxycarbonyl)cyclohexa-1,3-diene (2-b) is 253W, both Isolated as a yellow oil.
The DMAD conversion rate is 80%, and the selectivity based on reacted DMAD is (2-a)/(2-b)-40/60
It was hot.

The spectral data of the product is also shown in Table 3.

Example 10 (1,5-cyclooctadiene)(tetracyanoethylene)palladium(Dba)3Pd2(14
0ヮ; 0.153 mm01) and tetracyanoethylene (50.4 mm; 0.393 mm01).
5-cyclooctadiene (581m9; 5.37mm0
A solution of 1) in acetone (10 ml) was added at room temperature.

After stirring for 3 hours, the deep reddish-purple suspension gradually turned into a yellowish brown solution.

The solution was filtered and concentrated under reduced pressure to about 2 ml, and ethyl ether (0.5 ml) was added to the remaining orange solution. 47.9 Immediately (yield 4
6%) was obtained. M. p. 2O2~203℃ (Dec.
) IR spectrum: 2225 (1-1 (νCN) NMR
Spectrum (CDCl3) τ value; 3.91 (S・4, 1
．． 5-cyclooctadiene olefin proton), 7
．． 94 (Sl8, 1,5-cyclooctadiene) Elemental analysis as Cl4Hl2N4Pd Example 11 (Norbornadiene) (tetracyanoethylene) Palladium (Dba)3Pd2 (150W; 0.164mm0
1), tetracyanoethylene (41.4m9; 0.32
Using a solution of 3mm01) and norbornadiene (0.6m0 in benzene (5ml)), the same procedure as in Example 10 was performed to obtain deep yellow (norbornadiene)(tetracyanoethylene)palladium 367r9 (yield 36%).

M. p. 2l8~220℃ (Dec.) IR spectrum; 2265, 2225C! RL-1(ν
CN) Elemental analysis Example as Cl3H8N4Pd+1/6C6H6
12 (synchropentadiene) (tetracyanoethylene) palladium In Example 10, (Dba)3Pd is 150771y (0.164mm01), tetracyanoethylene is 78.8η (0.614mm01), and 1
・5-cyclooctadiene is converted into synchropentadiene (6
14～;4.64mm01) in exactly the same manner except that (synchropentadiene) (
Tetracyanoethylene)palladium was obtained in an amount of 54.4 times (yield: 45%).

M. p. 295-298°C (Dec.) IR spectrum; 2260, 2220 (7rL-1 (ν
CN) Elemental analysis as Cl6Hl2N4Pd Example 13 The utility of the present invention is illustrated by this example.

Bis(t-butyl isocyanide)palladium(0)Pd
Although (t-C4H9NC)2 is known to be effective in various catalytic reaction systems, conventional methods for its synthesis have been complicated. [J. Am. Chem. SOc., 91, 6994
(1969)] i.e. from sodium tetrachloropalladate via di-1 μm chloro-bis(η-allyl)nipalladium ([[) and η-allyl(η-cyclopentadienyl)palladium ([[)] This required long procedures and dangerous operations involving handling carbon oxide, metallic sodium dispersion, etc.

However, by using the novel palladium complex compound according to the present invention, the target substance can be easily and safely produced.

That is, 1.0 mm of (1,5-cyclooctadiene) (maleic anhydride) palladium (0) was dissolved in 15 ml of acetone-pentane (2/1), and 2 t-butyl isocyanide was dissolved at room temperature under a nitrogen stream. Add .5mn101.
Addition of a further 100 ml of pentane to the resulting pale yellow solution gives rise to an orange-red precipitate. This solid was filtered, washed with pentane, dried and made into 0.61mm01 bis(
t-Butyl)palladium(0) isocyanide was obtained. Example 14 Journal of Organometallic Chemistry (D.
Organ Ometallic Chainllstry7
Chloroform adduct of tris(tribenzylideneacetylacetone)tripalladium [hereinafter (Tbaa)3Pd3・CHCl3 produced by the method of the present inventors described in Vol. 3, p. 411 (19, 1974, Netherlands)
]0.127mm01 and maleic anhydride 1.0
9mm01 was placed in a 20ml round-bottomed flask, and after purging with argon, 3.0ml of dichloromethane was added under a nitrogen atmosphere.
Add m1 and stir.

Then, 4.0 ml of cyclohexene was added and stirred. After one hour it is still a dark reddish-brown heterogeneous solution. Furthermore, 2.0 ml of dichloromethane is added and stirred. Since there was no change, a reddish-purple homogeneous solution was obtained by passing through P. 2.0 ml of cyclohexene was added, cooled to -300 to 40'C, and the solvent was slowly removed under reduced pressure. Approximately 0.5
After concentrating to about ml, add 0.5 ml of cyclohexene and about 10 mj of ether, and cool to about -50°C. When the mixture was left to stand for about 15 minutes, white needle-like crystals were precipitated.
Further, ether was added to completely precipitate the complex, and the mixture was thoroughly filtered. The same product as in Example 1 was obtained.

Yield 85.71 (0.223 mm01) Yield 58% Example 15 (Tbaa)3Pd3・CHCl3, 0.0
883mm01 and dimethyl fumarate (hereinafter abbreviated as MF)
Take 0.649mm01 into a 10ml round bottom flask,
After replacing with argon, under nitrogen atmosphere, 1.0 ml of benzene
Add and stir.

Then, 1,5-cyclooctadiene (hereinafter referred to as 1,5-C
0.6 ml (abbreviated as OD) (4.88 TrLm01) was added and further stirred. After about 30 minutes, 1,5-CODlO
．． When 2 ml (1.63 mm 01) was added, the solution became a completely pale yellow-green homogeneous solution. After continuing stirring for another 30 minutes, the silica gel column prepared in advance (1
3cTrL×1.2? Pour the reaction solution directly into φ),
Benzene and hexane (5:1) in which 1,5-COD was dissolved
) Developed with a mixed solvent. The mixture is slowly developed with the same mixed solvent until the yellow band of tris(tribenzylideneacetylacetone)tripalladium (hereinafter abbreviated as Tbaa) is separated and distilled off.

After Tbaa was completely distilled off, the mixture was developed with acetone (50 ml) in which 1,5-COD was dissolved. When the solvent was distilled off from the obtained acetone solution under reduced pressure, a colorless oil was obtained. (This seems to be due to the inclusion of 1,5-COD). Add 10 ml of n-pentane, wash, and remove excess 1.
By removing 5-COD, the white solid (1.
5-COD) (MF) Palladium 70.73 (0.1
97mm01) was obtained. Yield 75% R spectrum;
2942, 1689, 1486, 1436, 1284,
1156, 1136, 1122? -1 Example 16 (Tbaa)3Pd3・CHCl3O. ll9mnlO
l and M.F. l. 78 mm of oil was placed in a 20 ml round-bottomed flask, and after purging with argon, 5.0 ml of dry benzene was added and stirred under a nitrogen atmosphere.

Next, Norbonnen (hereinafter abbreviated as NBE) 15.1mm
Stir the benzene (5.0 m0 solution) of 01. The solution gradually changes from dark reddish-purple to dark yellow-green, and becomes a completely yellow-green homogeneous solution after 20 minutes. Silica gel realumina 12
:1, 12 x 1.2? Pour this reaction solution into φ) and let it develop.

The developing solvent used was benzene (400ml) in which MF about 0.57 and NBE about 0.3y were dissolved, and Tbaa yellow 2<
Continue to flow slowly until the product is completely separated and distilled.
At this time, the column temperature is kept at 10°C or less. After Tbaa has completely distilled off, the column temperature is cooled to below 0°C (at this time, be careful not to solidify the benzene), and the column is developed with acetone (0°C, 150ml) in which a small amount of NBE is dissolved. The distilled acetone solution was obtained by removing the solvent under reduced pressure to obtain a white solid complex of 101.40η (0.23
0mm01) is obtained.

[crude (NBE)2(MF)Pd 64% yield], then N
Add 2.0 ml of acetone in which BE (approximately 0.3 y) is dissolved while cooling to completely dissolve the complex, and then slowly add ether dropwise until just before crystals precipitate.

If left in a cool place for a week, pale yellow crystals will form. 87.21wa (0.198mm01) [(MF)(NBE)2Pd 56% yield] is obtained.

MP~48℃Dec. IR spectrum: 2961, 29
46, 1705, 1501, 1491, 1434, 13
23, 1292, 114011026CT1L-1NM
R spectrum; Ha, . Hb,. Hh,. O. 89-1
．． 84, MllOHHcHdl2.66-3.34, M
l4H (Hc; 2.84, Ml2H,.Hd; 3.07
, Ml2H) Hil4.33, Bsl2HHglO. 5
l, Ml2H He1 4.26, m1 2H Hf1 4.79, m12H -OMe, 3.67, S, 6H (δ value, ppm) Example 17 (tbaa)3Pd3・CHCl3 0.130
20 mmol and 0.412 mmol of maleic anhydride
d in a round bottom flask, and after purging with argon, add 5.0 ml of acetone under a nitrogen atmosphere, and add NBDO. 5m
1 (4.94 mmol) and stir.

After 10 minutes, the solution gradually started to take on a green color, and after 20 minutes, it became a dark green, transparent, homogeneous solution.

After stirring for an additional 40 minutes, the mixture was filtered to remove a small amount of metal palladium, and the solvent was distilled off under reduced pressure. After concentrating to about 2 ml, 2 to 3 ml of ether was added, and a pale yellow powder was precipitated. Further, ether was added to completely precipitate the complex, which was then filtered, thoroughly washed with ether, and dried to obtain (norbornadiene) (maleic anhydride) palladium. Yield 101.467
ny (0.342 mmol) yield 88%m. p. 130
~132°C IR spectrum; 1815, 1750c TIL-1 elemental analysis (wt%) Example 18 as C11H1003Pd (tbaa)3Pd3・CHC13, 0.0944m
mol and 10.463 mmol of MF were placed in a 20 ml round bottom flask, and after replacing the flask with argon, 5.0 ml of acetone and 3.0 m2 of benzene were added and stirred under a nitrogen atmosphere.

Next, norbornadiene (hereinafter abbreviated as NBD) 0.2m
1 (1.98 mmol) and stir. The reddish-purple solution turned into a completely yellow-green homogeneous solution after 20 minutes. Stirring is continued further, and after 150 minutes, the solvent is distilled off under reduced pressure to concentrate to about 1.5 ml. This concentrated reaction solution was applied to a silica gel column (6cm x 1.7ClrLφ).
and develop a large excess of NBD with dissolved benzene. Benzene is continued to flow until the yellow band of tbaa separates and is completely distilled off. Approximately 100 ml was required.
Next, the column is cooled (below 0°C), and the complex is distilled off as quickly as possible using acetone (50m0) in which NBD is dissolved as the developing solvent. (At this time, some of the complex is separated in the column, and metal palladium A small amount of NBD is further added to the distilled acetone solution and the solvent is removed under reduced pressure.(NBD)(MF)palladium is obtained as a white powder, but it gradually decomposes in the air and becomes grayish white. Therefore, it is necessary to handle it under nitrogen. Yield: 88.63η (
0.259mmol1) Yield 91%m. p. 101-10
2°C (dec) IR spectrum: 29501 1710
, 1497, 1436, 1306, 1276, 1254
, 1225, 1195, 1152, 1026 cm Example 19 (tbaa)3Pd3・CHCl30.125 mmol1
was placed in a 20 ml round bottom flask, and after purging with argon, 5.0 ml of acetone was added and stirred under a nitrogen atmosphere.

Next, 0.1 ml of diethyl fumarate (hereinafter abbreviated as EF)
(0.612mm01) and NBD10.2ml (1.
98 mmol) and stir. The reddish-purple reaction solution gradually turned green, and after 2 hours it became a completely yellow-green homogeneous solution.

The reaction solution was placed in a silica gel column (15 x 1.2 cmφ) and slowly developed with a mixed solvent of benzene-hexane (5:1). The same solvent is used until the yellow band of tbaa is separated and distilled. At this time, mixed solvent (2
00ml), it is necessary to add 1 to 2 ml of NBD and about 1 ml of EF. In addition, the column temperature was 10
By keeping the temperature below ℃, decomposition of the chain in the column can be avoided. After tbaa was completely distilled off, the mixture was quickly developed with 50 ml of acetone in which NBD was dissolved to obtain an acetone solution of the complex. When the solvent of the collected solution is distilled off under reduced pressure, NBD can also be removed, but excess EF remains, so a colorless to pale yellow oil is obtained. By filtering, a white powder of (NBD)(EF) palladium is obtained. Yield 74.77 w (0.202 mm0
1) Yield 54% IR spectrum: 298011707,
1492, 1389, 1370, 1290, 1267,
1248, 1214, 115011094, 10380
1rL-1 Example 20 (Tbaa)3Pd3・CHCl3l97.6~(0.
1290 mm 01) was placed in a 10 ml round bottom flask that had been replaced with argon, 3 ml of dry acetone was added thereto, and the mixture was stirred at room temperature.

MF (1.2m1) and NBD (1.0m1) for 1m
Add with acetone from step 1. The reaction mixture changes from a dark purple suspension to a greenish-brown homogeneous solution after 10 minutes, and becomes a yellowish-green homogeneous solution after 20 minutes. This reaction mixture was put into a silica gel column (12 cm x 1?φ) and first developed slowly with a mixed solution of benzene (4) and hexane (1), and a yellow band was distilled out. This is tribenzylideneacetylacetone. At this point, when the column turns red (
Add NBD) and let it flow. After all the yellow band has been distilled off, it is quickly developed with dichloromethane-lyacetone (1:1 volume ratio). When the developing solution is solvent-distilled using a rotary evaporator and ether is added to the remaining oily substance, colorless powder (NBD) (MF) paudium is immediately produced. Yield 91~(yield 69%)M. p. 72-73℃ (Dec.
) IR spectrum; νCOl7l2cTrL-1 elemental analysis (wt%) as Cl3Hl6O4Pd (4) Average of two experimental values Example 21 (Tbaa)3Pd3・CHCl3l53.5η (0.
1002 mm01) is suspended in 1 ml of benzene under argon and 0.5 ml of methyl acrylate and 1 ml of NBD are added at room temperature with stirring.

After continued stirring for 30 minutes, the reaction mixture turned into a yellow-green homogeneous solution.

This solution was introduced into an alumina column (No. 1097 alumina Art9Ogel manufactured by Talc Corporation; 20 (11×1Cr!Lφ) and developed very slowly with a mixed solvent of benzene:n-hexane (4:1 volume ratio), and a yellow band was separated. I'm coming.

When this band has completely developed (if a red color is seen during this time, immediately add a small amount of methyl acrylate and (NBD) to the developing solvent) dichloromethane-lyacetone (1:
1 volume ratio) quickly flush out the complex with a mixed solvent. 60m
After concentrating 1, add ether and leave it in the refrigerator overnight to form an insoluble complex in the form of a white powder.

▲ When filtered and dried, 41 w (yield: 48%) of white powder (NBD) (methyl acrylate) palladium is obtained. p. 8l~84°C (Dec) IR spectrum: νCOl7O6cm-1 elemental analysis (wt%) Example 22 as CllHl4O2Pd (Tbaa)3Pd3・CHCl3289.8 (0.
1892mm01) was suspended in 1.5 ml of benzene, and at room temperature, 1 ml (7) NBD and 0.8 ml of distilled purified methyl vinyl ketone were added and stirred.

After about 10 minutes, the solution turns into a yellow homogeneous solution. After stirring at room temperature for 1 hour, an alumina column (Talc Co., Ltd. 109
It was introduced into No. 7 Art9O alumina:12 (7L x 1C7nφ) and developed with a mixed solvent of benzenelihexane (volume 3:1 ratio) to which a small amount of methyl vinyl ketone was added.

After the produced yellow band (Tbaa) is completely removed, the column is cooled to -10°C and developed under nitrogen with a mixed solvent of acetone lydichloromethane (1:1 volume ratio). After concentrating the developing solution under reduced pressure, the resulting oily substance (about 1 ml)
Add ether to the mixture and leave it in the refrigerator overnight to obtain insoluble (NBD) (methyl vinyl ketone) palladium in the form of a colorless powder. Yield 76.6 w (yield 50%) M. p. 67℃ (
Dec) IR spectrum; νCOl659C:r! L-1 elemental analysis (wt%) as CllHl4OPd (4) Average of two experimental values Example 23 (Tbaa)3Pd3.CHCl3O. lOlmmOl
and 0.620 mm01 of maleic anhydride were placed in a 10CC round-bottomed flask, and after replacing the flask with argon, 3.0 ml of acetone was added and stirred under a nitrogen atmosphere.

Synchropentadiene 0.3m1 (2.22mm01)
Add and stir further. After about 20 minutes, it becomes a yellow-green homogeneous solution. When stirring was continued, pale yellow microcrystals (needle-like) suddenly precipitated after 2 hours. ether 10
．． 0 ml was added, filtered, and the crystals were thoroughly washed with ether and dried to obtain (synchropentadiene) 2 (maleic anhydride) palladium. Yield 131.4
4~, (0.280mm01), yield 92%M. p. l
l4~117℃ IR spectrum; 1814, 1758C7! L-1 elemental analysis (wt%) Example 24 (Tbaa)3Pd3・CHCl3O. llOmmOl
and 1.06 mm01 (10 times MOI) of maleic anhydride were placed in a 10 ml round bottom flask, and after purging with argon, 1.0 WLI of benzene was added and stirred under a nitrogen atmosphere.

Claims (1)

[Claims] 1 General formula (I): Pd(L)_m(L')_n...
(I) (wherein L is an electron-donating olefin selected from the group consisting of cycloolefins and cycloalkadienes, and L' is an electron-accepting olefin selected from the group consisting of maleic anhydride, fumaronitrile, and tetracyanoethylene) A palladium complex compound represented by olefin, m and n represent 1 or 2). 2 Tris(dibenzylideneacetone)dipalladium (
O), an electron-donating olefin selected from the group consisting of cycloolefins and cycloalkadienes, and an electron-accepting olefin selected from the group consisting of maleic anhydride, fumaronitrile, and tetracyanoethylene. Featured general formula (I): Pd(L)_m
(L')_n・・・・・・・・・・・・(I) (In the formula, L is the above-mentioned electron-donating olefin, L' is the above-mentioned electron-accepting olefin, and m and n represent 1 or 2. ) A method for producing a palladium complex compound represented by 3. General formula (II): Pd(L)_m(L') characterized by reacting bis(fumaronitrile)palladium with an electron-donating olefin selected from the group consisting of cycloolefins and cycloalkadienes. ＿n・・・・・・
......(II) (wherein L is the above electron-donating olefin, L' is fumaronitrile, m and n are 1 or 2
represents. ) A method for producing a palladium complex compound represented by