Method for producing [Ir(cod)Cl]2

Details Method for producing [Ir(cod)Cl]2 Method for producing [Ir(cod)Cl]2

2001-01-09

2002-06-04

Shaver, Paul F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

Reexamination Certificate

active

06399804

ABSTRACT:

The invention relates to a method for producing [Ir(cod)Cl]
2
.
In the state of the art there are known several methods for producing [Ir(cod)Cl]
2
, namely by the methods of Herde (J. L. Herde, J. C. Lambert and C. V. Senoff: Inorganic Syntheses, 15 (1974), 18), Crabtree (R. H. Crabtree and G. E. Morris, J. Organomet. Chem., 135, 395 (1977), Winkhaus and Singer (Güinter Winkhaus, Hellmut Singer, Chem. Ber., 99 (1966) 3610), Pannetier, Bonnaire and Fougeroux (G. Pannetier, R. Bonnaire et P. Fougeroux, Journal of the Less-Common Metals, 21 91970), 437-438), and Bezman, Bird, Fraser and Osborn (S. A. Benzman, P. H. Bird, A. R. Fraser, J. A. Osborn, Inorganic Chemistry, 12, 1980, 3755).
Winkhaus and Singer obtained [Ir(cod)Cl]
2
in a 45% yield by reacting Na
2
IrCl
8
.6H
2
O or H
2
IrCl
8
.6H
2
O with cod in a mixture of water and ethanol after 8 to 12 hours of heating with refluxing. After the precipitated crystals were washed with methanol the compound was dried and redissolved in dichloromethane.
Pannetier, Bonnaire and Fougeroux obtained the complex in a yield of 85% by reacting H
2
IrCl
6
with cod in a mixture of water and ethanol after refluxing for 12 hours (no further information regarding the method of procedure).
Bezman, Bird, Fraser and Osborn describe the synthesis of [Ir(cod)Cl]
2
by a modified method of Winkhaus and Singer. Iridium trichloride hydrate, hydroquinone, ethanol, water and cycloocta-1,5-diene are refluxed for 4 hours. Then the solvent is partially distilled out and the precipitated product is filtered out, washed and dried. The yield is only 59%.
In Herde's method, iridium trichloride hydrate, ethanol, water and cycloocta-1,5-diene is refluxed for 12 hours. After cooling to room temperature the precipitated product is filtered out, washed and dried. A disadvantage of this method is the low yield of only 72%.
[Ir(cod)Cl]
2
is prepared by the Crabtree method, at first without the addition of water, and is then converted with aqueous sodium acetate to the desired complex compound, which is then recrystallized out of dichloromethane/ethanol. The yield in this case is 90-95%, but it entails a multi-step procedure which is therefore complicated and expensive.
From what as been stated, the problem arises of at least partially eliminating the above-stated disadvantages by means of a novel process. The present problem consists especially in offering a simple and thus less expensive method for the production of [Ir(cod)Cl]
2
in a high yield.
This problem is solved according to the invention by a method according to claim
1
.
In the method of the invention, first IrCl
4
.nH
2
O and/or IrCl
3
.nH
2
O and/or H
2
IrCl
6
are dissolved in water, then at least one alcohol of the formula R—OH wherein R=C
n
H
2n+1
and n=3−9, especially isopropanol, and cod (cycloocta-1,5-diene) are added and the solution is stirred at the boiling temperature.
Important to the invention in the proposed method is the use of at least one alcohol of the formula R—OH wherein R=C
n
H
2n+1
and n=3−9, especially isopropanol, which surprisingly in combination with water and cod has both good solvent properties as well as gives excellent precipitation of the end product. (The alkyl moieties of the alcohol are both straight-chain and branched moieties.)
The ordinary use of ethanol in the Herde process gives considerably lower yields (72%).
First, it is advantageous if the volumetric ratio of alcohol, especially isopropanol, to water is 2:1 to 1:1, since this ratio has proven good in practice both in regard to the solubility properties of iridium chloride, especially of IrCl
4
, and also in regard to the excellent properties of precipitation of the end product.
It is furthermore advantageous if the molecular ratio of iridium to cod is 1:8.6, since this ratio has proven good in practice.
After the solution is stirred at ebullition the resultant [Ir(cod)Cl]
2
is filtered out, washed and dried, the solution as a rule being first cooled to room temperature. Such a procedure permits an excellent separation of the [Ir(cod)Cl]
2
from the solution.
It is furthermore advantageous, since it has been proved, if the filter cake (the desired end product) is washed with methanol, especially with cold methanol, and then dried.
Lastly, the residual solution freed from the precipitate is again concentrated in an advantageous manner, to about 30 to 50% of its original volume and the precipitate obtained is again filtered out, washed and dried, in order thus to increase the total yield.
It is furthermore advantageous if the [Ir(cod)Cl]
2
product is ground to a maximum grain size of about 0.4 mm, since this coarse powder has good handling properties, such as a satisfactory weigh-out ability.
The following examples serve to explain the invention:


REFERENCES:
patent: 6197716 (2001-03-01), Baumeister et al.
Inorganic Syntheses, vol. XV (1974), pp. 18-20.
Inorganic Syntheses, vol. XIV (1973), pp. 92-95.
Journal of Organometallic chemistry, 135 (1977), pp. 395-403.
Chemische Berichte, 99. Jahrg./1966/Nr. 10, pp. 3610-3619.
Chemical Abstracts, vol. 97, 1982, p. 668.

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