DE1768223C - Process for the preparation of polynuclear complexes of transition metals of VI. to VIII. group of the periodic table - Google Patents

Description

Divalent bridged transition metal complexes, * in which the metals are different, as well as their j, production and use as catalysts has already been proposed.

Now a process for the production of polynuclear complexes of transition metals of the VI. to VIII. Group of the periodic table found, which is characterized in that a π-complex a transition metal of the VI. to VIII. Group, the reactive group optionally attached to the metal Has bonded alkyl radical, with a complex of a transition metal of VI. to VIII. group, the contains at least one reactive hydrogen that is bound to the metal or to a phosphine, Arsine or stibine ligands is bound, converts.

The transition metal 7r complex is shown below referred to as the "hydrocarbon complex". The second transition metal complex, the at least one contains reactive hydrogen is referred to as a "hydrogen-containing complex". As »Coal water- 20: serstoffligand «becomes either a.-r-bonded hydrocarbon or its anion or an alkyl radical.

It is believed that the reaction proceeds with removal of the hydrocarbon ligand along with the hydrogen from the hydrogen-containing complex proceeds as a free hydrocarbon, wherein, the remaining fragments condense to form a single compound. Free hydrocarbon can determined in the reaction products, for example, by gas-liquid chromatography will.

The process according to the invention can be carried out by reacting a mononuclear hydrocarbon complex, which contains only a single hydrocarbon ligand, with a mononuclear hydrogen containing complex, which also contains only one reactive hydrogen, are carried out. For example, π-allylmanganese tetracarbonyl can with Hydridomanganese pentacarbonyl or Diphenylphosphineisentetracarbonyl be implemented, with propylene and binuclear complexes with two manganese atoms or one manganese and one Iron atom can be obtained. Trinuclear complexes can be produced by reacting a mononuclear hydrocarbon complex, containing two hydrocarbon ligands, with a hydrogen-containing complex containing only one reactive hydrogen has to be produced.

Tetranuclear complexes can consist of binuclear hydrocarbon complexes in which at least a hydrocarbon ligand is attached to each metal atom by reacting with only one reactive hydrogen-containing complex are produced. For example, a -r-allyl palladium chloride dimer reacts with diphenylphosphinechromopentacarbonyl to form a tetranuclear complex, whereby propylene is released.

The reaction takes place in inert solvents such as ethers or aromatic hydrocarbons performed. Suitable solvents are e.g. B. tetrahydrofuran and benzene. The reactions are running usually rapid, with frequent color changes. The reaction temperature is preferably room temperature, although higher or lower temperatures are used be able. Precautions should be taken to avoid air and moisture during the rerunning Avoid reaction, for example by performing the process in a nitrogen atmosphere. The products, which are generally stable to air, can be prepared by customary procedures, such as filtration, crystallization and chromatography, purified and isolated. ,

The complexes prepared according to the invention can be used as catalysts for hydrogenations. It are multi-purpose catalysts with different metals, each of which has its own specific function, available. On the other hand, complexes for use as catalysts can be prepared in those an expensive metal, like platinum or palladium, in a complex with a cheaper metal, like Iron, is combined. It is often found that the dilution of the expensive metal does not occur a corresponding loss of catalytic activity is achieved.

In the following examples all reactions were carried out under nitrogen. Solvents were as follows cleaned and dried: tetrahydrofuran was subdivided by sodium and ben ^ ophenon Nitrogen was distilled off, and benzene and toluene were dried over sodium.

example 1

0.2 g of a dimeric. -T-allyl palladium chloride and 0.42 g of biphenylphosphinechromopentacarbonyl were dissolved in 50 ml of tetrahydrofuran. After 1 hour the color changed to yellow-brown and after 3 hours the color was red-brown. After standing overnight, a black solid was removed by filtration. The red filtrate was concentrated under reduced pressure and gasoline was added to induce crystallization. The red powder obtained had infrared carbonyl absorption bands (Niijol) at 1955 and 2035 cm " ^1. Propylene was evolved during the reaction and identified by gas-liquid chromatography of the reaction solution. The analytical values agreed with those of a compound of the following structure .

Ph,

(OC) ₅ Cr

Pd

Cl

Pd

Cr (CO) ₅

Ph ₂

Example 2

0.2 g of a dimeric ethylene platinum dichloride and 0.24 g of diphenylphosphine iron tetracarbonyl were reacted with one another in 40 ml of tetrahydrofuran. The solution quickly changed color to dark brown. Concentration under reduced pressure and the addition of gasoline gave 0.23 g of a brown solid complex containing platinum and iron and having infrared absorption bands (Nujol) at 1980, 2005, 2055 cm " ¹ .

Example 3

0.1 g of a dimeric π-allylpalladium chloride and 0.195 g of diphenylphosphine iron tetracarbonyl was dissolved in tetrahydrofuran. The solution changed hers Color from yellow to red in about 5 minutes. The solution

was allowed to stand for 3 days and most of the solvent was removed under reduced pressure. Petrol was added, giving 0.25 g of a product as a red solid with a melting point of 90 to 95 "C and infrared absorption bands (Nujol) at 955, 2000 and 2030 cm" ¹ . Molecular weight: found: 1008; calculated 990. The properties of this product were in accordance with the formula given below.

Further, the product was recrystallized from toluene to give red crystals with one molecule Obtain crystal toluene.

Elemental analysis:
Found:

C 43.1, H 3.1, Cl.6.7, Fe 10.2, P.6.3, Pd 18.7%; calculated for C ₃₉ H ₂₈ Cl ₂ Fe ₂ O ₈ P ₂ Pd ₂ :

C 43.0, H 2.6, Cl 6.5, Fe 10.2, P 5.7, Pd 19.6%.

Propylene evolved during the reaction, which was determined by gas / liquid chromatographic analysis of the Reaction solution has been identified,

(OC) ₄ Fe Pd Pd Fe (CO) ₄

Cl P

I.

Ph ₂

The structural formula given above was determined by X-ray structure analysis.

B e i s ρ i e 1 4

0.20 g of cyclooctadiene palladium dichloride and 0.2 mg of diphenylphosphine iron tetracarbonyl were stirred in tetrahydrofuran. A rapid reaction took place and the mixture turned yellow-orange and then red. A small amount of a black solid (5 mg) was removed by filtration. The red filtrate was concentrated and methylcyclohexane added to give 0.30 g of a red powder which decomposed at 230 ° C. Elemental Analysis C 34.0; H 3.6; Cl 15.9; P 6.7; Pd 18.2; Fe 14.3%; the IR carbonyl absorption bands (Nujol) were at 1970, 2000, 2010, 2080 cm " ^1. The proton nuclear magnetic resonance spectroscopy showed that no cyclooctadiene remained in the solid product although it was present in the reaction solution. It is assumed that the product with that of example 3 is identical.

Example 5

0.3 g of a dimeric diallylchlororhodium and 0.975 g of diphenylphosphine iron tetiracarbonyl were stirred in 80 ml of benzene. The yellow solution turned dark brown within 1 hour. Gas / liquid chromatographic analysis showed that both propylene and diallyl had evolved. The majority of the solvent was removed and the residue extracted with benzene, filtered and evaporated the mother liquor to give a red-brown powder with infrared - carbonyl - ER absorption bands (nujol) at 1815, 1960, 1985, 2000 and 2050 cm ^{"1 6} S gave.

Elemental analysis: C46.7, H3.7, Cl3.6, P8.1, Fe 11.0,

UV, O QO /

Example 6

Molar equivalents of a dimeric diallylchlororhodium and hydridomanganese pentacarbonyl were stirred in tetrahydrofuran. Gas / liquid chromatographic analysis showed that propylene had evolved. The yellow solution quickly changed to red. Evaporation of the mother liquor and addition of light petroleum gave a solid product with infrared carbonyl absorption bands (Nujol) at 1910 (s, b), 1985 (w), 2003 (m) and 2060 (W) Cm " ¹ .

Example 7

0.5 g of π-allylmanganese tetracarbonyl and 1 molar equivalent of hydridomanganese pentacarbonyl were stirred in tetrahydrofuran. Gas / liquid chromatographic analysis showed that propylene had evolved. Evaporation of the mother liquor and addition of light petroleum gave 0.134 g of a yellow solid which decomposed at 130 to 135 ° C and carbonyl infrared absorption bands (Nujol) at 1860 (m, s), 1900 (s), 1990 (s) and 2040 (m, s) cm " ¹ .

Example 8

0.25 g of ^ cyclopentadienyl triphenylphosphine nickel methyl and 1 mol equivalent of hydridomanganese pentacarbonyl were stirred in tetrahydrofuran. Gas / liquid chromatographic analysis showed that methane had evolved. Evaporation of the solvent and addition of light petroleum gave 0.13 g of a yellow-brown solid which decomposed at 150 ° C and carbonyl absorption bands (Nujol) in the infrared spectrum at 1905 (s, b), 1985 (m, w) and 2030 (m , a) cm " ¹ .

Example 9

Each 1 molar equivalent of π-allyl molybdenum dicarbonylbipyridyl chloride and hydridomanganese pentacarbonyl were stirred in methyl ethyl ketone. Gab / liquid chromatographic analysis showed that Propylene had evolved, but the starting material was not completely soluble and contaminated the product.

Example 10

1.04 g of π-allyl manganese tetracarbonyl and 1.77 g of diphenylphosphine iron tetracarbony 1 were stirred and refluxed in toluene for 4 hours. Evaporation of the solvent gave an oil which was dissolved in added ether and hexane. Ether was removed under vacuum and the resulting red-brown solid removed by filtration. The product had a melting point of 160 to 165 ° C, and its mass spectrum showed Tür that

Molecular ion one signal at -j = 519 and other signals at 295 (-8CO) 239, 183, 163, 142, 167, 78 in accordance with the formula

PPh ₂ MnFe (CO) ₈ .

Elemental analysis: found: C 46.1, H 2.05%.
Calculated for C ₂₀ Hi _{0 FeMnO 8} P: C 46.1, H 1.9%.

and 55-,

• Fe (CO) ₄

ίο

15th

20th

The analytical data agreed with the following structural formula:

(OC) ₄ Mn ¹ ^ Fe (CO) ₄

Example 11

2.6 g of π-AlIyIkobalttricarbonyl and 5.0 g Diphenylphosphineisentetracarbonyl were stirred for 3 hours in toluene and heated at 8O ⁰ C. Evaporation of the solvent under reduced pressure gave a red-brown oil. After addition of methylcyclohexane and purification by chromatography over silica gel, a solid was obtained with IR carbonyl absorption bands at 2070 (m), 2C50 (m), 2020 (s), 2000 (s), 1970 (s) and 1920 (s). Recrystallization from tetrahydrofuran-methylcyclohexane gave a solid, the elemental analysis of which gave the following:

Found: C 46.2, H 3.8, P 7.7, Fe 10.9%.

FUrC ₁₉ H ₁₀ CoFeO ₇ P

Calculated: C 45.9, H 2.0, P 6.4, Fe 11.2%.

The analytical data agreed with the following structural formula:

Ph ₂

(OC) ₄ Fe -Co (CO) ₃

Example 12

0.20 g Ti-cyclopentadienyl triphenylphosphine nickel methyl and 0.18 g of diphenylphosphine iron tetracarbonyl were stirred in tetrahydrofuran. Gas / liquid chromatography showed that methane was evolved had. The tan solution was concentrated under reduced pressure and a petroleum ether was added to induce crystallization of the product.

The product obtained was a light brown powder (0.12 g) with IR carbonyl absorption bands (Nujol) at 1930 (s), 1970 (m) and 2040 cm " ^1. The signals of the nuclear magnetic proton resonance were at 2.14 and 2 , 87 r.

The elemental analysis showed:

found: Ni 7.4, Fe 7.7%.

FUrC ₃₉ H ₄₀ NiFeO ₄ P ₂ :
calculated: Ni 7.9, Fe 7.7%.

The analytical data agreed with the following structural formula:

It quickly turned red and eventually turned deep red-brown. Gas / liquid chromatographic analysis showed that propylene had evolved. The resulting solution was concentrated under reduced pressure and methylcyclohexane was added to induce crystallization. 0.504 g of product was obtained as a red-brown powder which had IR carbonyl absorption bands (Nujol) at 1935 (s, b), 2040 (w) and 2060 (w) cm " ¹ .

Elemental analysis:

found: C 29.8, H 2.4, Cl 6.7, P 4.1%.
FUrC ₃₄ H ₂₀ Cl ₂ P ₂ Pd ₂ O ₁₀ W ₂ :

Calculated: C 31.3, H 1.5, Cl 5.4, P 4.8%.

The analytical data agreed with the following structural formula:

Ph,

(OQ ₅ W

Cl

Pd

Pd

W (CO) ₅

30th

35 ν γ

Ph ₂

Example 14

0.46 g of diphenylphosphine molybdenum pentacarbonyl and 0.20 g of π-allyl palladium chloride were stirred in benzene. The reaction occurred immediately and the solution turned dark brown. Some precipitation occurred after _{1/2 hour.} The solution was evaporated to a small volume and light petroleum was added to give 0.34 g of a dark brown powder with IR carbonyl infrared absorption bands (Nujol) at 1840 (s) and 1940 (s) cm " ¹ .

The analytical data agreed with the following structural formula:

Ph ₂

Ph,

(OC) ₄ mo

.Cl

Pd

Pd

C Cl " C

Mo (CO) ₄

55

Claims (1)

Claim: 60 Example 13 0.79 g of diphenylphosphine tungstacarbonyl and 0.20 g of dimeric π-allyl palladium chloride were in Benzene stirred for 1 hour. The yellow solution changed processes for the production of polynuclear complexes of transition metals of the VI. to VIII. Group of the Periodic Table, thereby characterized in that one has a π complex a transition metal of the VI. to VIII. Group, which may be used as a reactive group has an alkyl radical bonded to the metal, with a complex of a transition metal the VI. to VIII. Group which contains at least one reactive hydrogen, the is bound to the metal or to a phosphine, arsine or stibine ligand.