DE2116226C3 - Process for the preparation of iron complexes - Google Patents

Description

CO

C ₁ H ₅ Fe-C =
CO

Y-

in which Y is BF ₄ , PF ₆ , Cl or B (C ₆ H ₅ I _4. 2. Process according to Claim 1, characterized in that the reaction is carried out in the presence of tetrahydrofuran, dichloromethane or diethyl ether.

The invention relates to a process for the preparation of elsene complexes, which is characterized in that a nucleophilic agent from the group N ₃ ", N ₂ H ₄ , N ₂ H ₃ R, NH ₂ R, R0 ~, NCS", where R is an alkyl or aryl radical, is reacted with an iron complex of the general formula at a temperature of 20 to 60 ° C., optionally in the presence of an inert solvent

CO
C ₅ H ₅ Fe-C =

In which Y is BF ₄ , PF ₆ , Cl or B (C ₆ H ₅ ).

With the method of the invention it is possible for the first time in a relatively simple and economical way And way of introducing the CS group into organic compounds and making compounds that hitherto f) were difficult to synthesize.

M. Du bin "Organometallic Compounds", Vol. I, 2nd edition (1966), p. 201, has already described the production of C ₅ H ₅ Fe (CO) ₂ CI, the chlorine atom of which in methanolic solution CN "can be tubstituted, but there is no mention of the introduction of a CS group. This also applies to that of EO Fischer and H. Werner in" Metall-Tt-Koinplexe ... ", 1962, p. 31, The process described for the preparation of a cyclopentadienyl _{iron dicarbonyl complex by reacting C 5} H ₅ Fe (CO) ₂ Cl with triphenylphosphine in the presence of a reducing agent such as sodium borohydride. Group in the iron complex.

The inventive method of the type characterized above has compared to the known Process has the advantage that it is possible under very mild conditions that are desirable for many purposes Introduce CS group into organic compounds, with the desired products in high yields can be obtained. This makes it possible for the first time to use iron complexes containing a CS group easy and cheap to manufacture in a technical way.

The process according to the invention is carried out within the range from 20 to 60 ° C, preferably at room temperature, accomplished. The inventive method

can drive without the use of a solvent, whereby the nucleophilic agent used is itself as Solvent acts, or in the presence of an inert solvent, for example in the presence of vcn Tetrahydrofuran, dichloromethane or ethyl ether.

be performed.

The reaction products that are increased by the process according to the invention are different, depending on what nucleophilic agent are used i. This is evident from the following reaction equations

which are intended to explain the invention in more detail

1. [C ₅ H ₅ Fe (CO) ₂ CS] ^ N ₃ -

-> C ₅ H ₅ Fe (CO) ₂ NCS + N ₂

2. [C ₅ H ₅ Fe (CO) ₂ CS] ⁺ + NH ₂ - NH ₂

- ^ C ₅ H ₅ Fe (CO) ₂ NCS + NH ₃ + H ¹

3. [C ₅ H ₅ Fe (CO) ₂ CS] ⁺ + RO "

-> C ₅ H ₅ Fe (CO) ₂ COR

4. [C ₅ H ₅ Fe (CO) ₂ CS] ⁺ + 2 NH ₂ R

-> C ₅ H ₅ Fe (CO) ₂ CNHR + NH ₃ R ⁺

The following examples are intended to illustrate the invention.

example 1

A solution of 0.0325 g (0.5 mfvl) of NaN ₃ in 3 ml of water was added, with stirring, to a solution of 0.183 g (0.5 mmol) of [C ₅ H ₅ Fe (CO) ₂ CS] PF ₈ in 30 ml

Acetone added. Nitrogen was immediately evolved and the solution changed color from yellow to dark red. After stirring for 15 minutes at room temperature, the acetone was removed using a rotary evaporator and the residue was treated with 15 ml of water. The C ₅ H ₅ Fe (CO) ₃ NCS was extracted from the resulting mixture by 20 ml of CHCl ₃ and the solution was dried _{over CaCl 2.} The chloroform was evaporated to 5 ml, then 50 ml of hexane was added _{to make C 5} H ₅ Fe (OC) _{2 NCS.} The yield was 55%. The compound was red in color and had a melting point of 118 to 119 ^° C. The elemental analysis gave the following results:

Calculated .... C 40.9, H 2.1, N 6.0, S 13.6%;
found .... C 40.5, H 2.3, N 5.9, S 13.9%.

Example 2

A solution of 0.183 g (0.5 mmol)

[C ₅ H ₅ Fe (CO) ₂ CS] PF,
and 0.05 ml (1 mmol NH ₂ - NH ₂ in CH ₈ Cl ₂ was added

reacted at room temperature with stirring and in a nitrogen atmosphere. The reaction mixture immediately turned red. After 30 minutes the solvent was removed by evaporation in vacuo and the residue was dissolved in 20 ml CHCl ₃ and then filtered. The resulting solution was concentrated and then pentene was added. In this way, C ₅ H ₅ Fe (CO) ₅ NCS was obtained in 35% yield.

Example 3

A mixture of 1 g of [C ₅ H ₅ Fe (CO) ₂ ] PF ₆ in 50 ml of anhydrous methyl alcohol was stirred for 20 minutes at room temperature in a nitrogen atmosphere and in the presence of excess Na ₂ CO _3. The solution was filtered and the solvent evaporated under reduced pressure to give a brownish yellow residue which was then dissolved in 20 ml of ether and then filtered. The solvent was removed, the product obtained was sublimed in vacuo at 40.degree. C., and at the end an orange substance with a melting point of 75 to 76.degree. C. was obtained. The yield on

C ₅ H ₅ Fe (CO) ₂ CSOCH ₃

was 70%. The elemental analysis provided the following values:

Calculated ... C 42.9, H 3.2, S 12.7%;

found .... C 43.1, H 3.0, S 12.6%.

Example 4

In a suspension of 0.5 g of [C ₁ HiFe (CO) ₂ CS] PF ₀ in 50 ml of ethyl ether, saturated with nitrogen, was

Methylamine initiated. The reaction was stopped after 20 minutes and the solution was filtered. The filtrate was evaporated under reduced pressure. A brown oil was obtained as residue. Its hexane spectrum showed two strong absorptions at 2C07 and 1965 cm, which refer to the stretching vibrations of the terminal CO groups, and an absorption at 1158 cm ~ \ which is due to the Stretching vibration of the CS group decreases.

It was not possible _{to isolate the thiocarbon complex C 5} H ₅ Fe (CO) ₂ -CSNHCH ₃ , but after treatment with HCl the starting thiocarbonyl complex was obtained.

Example 5

ao At room temperature, 1 mmol RCNS / u of a solution of [C _s H ₅ Fe (CO) ₂ CS] PF ₆ in 20 ml of dry acetone was added. The resulting mixture was stirred for 1 hour. The solvent was evaporated in vacuo giving a

The red residue was obtained, which was dissolved in CHCl ₃ and filtered. Then the resulting solution was dried down to 10 ml. When pentane was added, (20 °, ₀ ) C ₅ H ₅ Fe (CO) ₂ CN were obtained in low yield.

Claims (1)

Patent claims: 1. A process for the preparation of iron complexes, characterized in that a nucleophilic agent from the group N ₃ ", N ₂ H ₄ , N ₂ H ₃ R, NH ₂ R, RO ~, NCS-, wherein R is an alkyl or Aryl radical means, at a temperature of 20 to 60 ° C, optionally in the presence of an inert solvent, reacted with an iron complex of the general formula