DE2116226A1 - Process for the preparation of iron complexes - Google Patents

Description

Oasis 37V372 - Comm. 5087 «08

SNAM PROGETTI Sop.A. Hailand, 'Italy

Process for the preparation of iron complexes

The invention relates to a method for producing special Iron complexes. In particular, it relates to a process for the preparation of some special iron complexes, which includes nucleophilic reactions on cationic iron complexes,

Iron complexes are known to have the general formula

¹ CO L
* C0

in which L is a ligand consisting of both a saturated compound, such as phosphine, arsine or derivatives thereof, and an unsaturated compound such as, for example, B, CS, CH ₂ -CH ₂ or CH ₂ - CHR, in which R is an alkyl or aryl radical,

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and Y "" is a negative ion such as e.g. B. Cl ", B (GgH, -) ^ etc." mean.

It has now been found that it is possible to use iron complexes easily and cheaply in a very technical manner to synthesize »

The process according to the invention is characterized in that an iron complex, as indicated above, is ^{hydrazine substituted with a nucleophilic agent from the group N * ", NHg" * 1} ^ ', the primary and secondary amines »alkoxy groups, IfCO"", NGS "*, GK", which converts acetate ions etc. <, Pur if L means an unsaturated ligand, it can also contain more than one unsaturation »

The reaction products are different o © according to the used nucleophilic agent, which can be seen from the following reaction equations, which are intended to explain the invention.

1.) CO ₅ H ₅ Fe (GO) ₂ CS] * + N ₅ "- i> O ₅ H ₅ Fe (OO) ₂ NCS + N ₂

2.) [G ₅ H ₅ Fe (GO) ₂ GS] ⁺ + HH ₂ -NH ₂ - ■> C ₅ H ₅ Fe (OO) ₂ NOu + NH ₅ + H ⁺

3.) CC ₅ H ₅ Fe (OO) ₂ Co] * + HO

4.) ECcH ₁ -Fe (CO) ₀ CS] ⁺ + 2NH ₃ R - ■ $> C ₁ -H ₁ -Fe (CO) ₀ CNHR + NH ₂ R ⁺

5.) [C ₅ H ₅ Fe (CO) ₂ (CH ₂ = CH ₂ )] ⁺ + RH ₂ R - £> C ₅ H ₅ Fe (CO) ₂ -

CH ₂ CH ₂ NHMI ⁺

6.) [C ₅ H ₅ Fe (CO) ₂ (CH ₂ = CH ₂ )] ⁺ + RO "- ^> C ₅ H ₅ Fe (CO) ₂ -GH ₂ -CH ₂ OR 7.) CG ₅ H ₅ Fe (CO) ₂ L] ⁺ + 2NH ₂ -NH ₂ - £> C ₅ H ₅ Fe (CO) L (NOO) + MH ₃ -SH

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8.) CC ₅ H ₅ Pe (CO) ₂ LI ⁺ + 2Im ₂ -NHR - ^ G ₅ H ₅ Fe (CO) L (NCO) + H ₂ HR + H ⁺ 9c) [C ₅ H ₅ Fe (CO ) ₂ L] ⁺ + N ₅ "- ~> C ₅ H ₅ Fe (CO) L (NCO) + N ₂

The last three examples relate to complexes in which L is a saturated ligand.

The method according to the invention is carried out at a temperature within the range from 20 to 50 ° <? » preferably at Saumtemperatur, in the presence of e. ° ~ _t it against the nucleophilic reaction inert solvents such. B. carried out in the presence of tetrahydrofuran, dichloroethane, ether or in the presence of the nucleophilic agent itself as a solvent "

Another object of the invention is that the ligand of the ethylene type and the iron complex obtained as indicated above from the action of Carbanionverbinduugeu * rie z. B · R, C ⁺ Y ", in which R and Ύ have the meanings given above, this compound being converted into an unsaturated complex in which the remainder of the nucleophilic agent is added to the unsaturated bond.

The reaction is carried out in inert solvents at room temperature according to the following equation:

, co

--CH ₂ -CH ₂ X + R ₅ C ⁺ --->

c.

+ R ₂ CH 5

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where X is one of the abovementioned nucleophilic agents and E has the known meaning _o

When the thus obtained unsaturated complex is exposed to thermal radiation or light radiation or with unsaturated Compounds is reacted at high temperature and high pressure, the VinyT compound is released and in the In the second case the iron starting complex arises again. the Implementation is very beneficial due to the possibility of very large amounts of vinyl compound from small amounts of the iron complex. The above implementation is quite general, since it also applies to other cationic ones

Complexes of transition metals can be used, which form coordination complexes with olefinic groups «.

Some further working characteristics emerge from the following examples, which are merely illustrative of the invention should without, however, restricting them to that.

example 1

A solution of 0.0325 g _(0? 5 mmol) was dissolved in 3 ml of water NaISL under Eühren to a solution of 0 * 183 g (0.5 mmol) [C ₅ H ₅ Fe (CO) ₂ -CS] PFG in 30 ml of acetone were added. Nitrogen was immediately evolved and the solution changed its color from yellow to P dark red. After stirring for 15 minutes at room temperature, the acetone was removed with the aid of a rotary evaporator and 15 ml of water were added to the residue. The C ₁ -H _1-Fe (CO) ₂ NCS was extracted by 20 ml CHCl, from the mixture obtained and the solution was dried over CaCIp _o The chloroform was evaporated down to 5 ml is then were used to prepare C ^ H ₅ Fe (OC) ₂ NOS 50 ml of hexane added The yield was 55% The compound had a very fine red color and a melting point of 118 to 119 ^σ 0 _ο , the elemental analysis gave the following results:

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ber .: C 40 »9 H 2.1 N 6th , 0 S. 13th , 6 found: 40 .5 2.3 5 »9 13th .9 Example 2

A solution of O _S 183 g (0 _$ 5 mmol) of ₅ H ₅ CO Pe (OO) ₂ CS] PF _6, and 0.05 ml (ImMoI) KH ₂ -M ₂ in GH ₂ Ol ₂ was treated at room temperature with stirring and reacted 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 of CHCl 2 and then filtered. The resulting solution was concentrated and then pentane was added. In this way, O ₅ H ₅ Fe (CO) ₂ -NGS was obtained in 35% yield.

Example 3

A mixture of 1 g of CO ₅ H ₅ Fe (CO) ₂ OS] 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} The solvent was evaporated off under reduced pressure, giving a brown-yellow residue which was then dissolved in 20 ml of ether and then filtered. The solvent was removed, the product obtained was ^{sublimed under vacuum at 40 °} C. and an orange color was obtained at the end Substance with a melting point of 75 to 76 ° C · The yield of C ₅ H ₅ Fe (CO) ₂ CSOOH ₅ was 70%. The elemental analysis provided the following values:

ber .: C 42 _t 9 H 3 , 2 S. 12th , 7 found: 43.1 3 , 0 12th , 6 Example 4

From C ₅ H ₅ Fe (OO) ₂ C (S) OC ₂ H ₅ J, working in ethyl

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alcohol using the same procedure as described in the previous example,

₅₅₅ The infrared spectrum in CS- gave the following result: V (CO) at 2031 and 1980 cm "^ and V (CS) at 1172 cm" ¹ .

Example 5

Methylamine was passed into a suspension of 0.5 g of CC ₅ HcFe (CO) ₂ CS] PP ₆ in 50 ml of ethyl ether, saturated with nitrogen. The reaction was stopped after 20 minutes and the solution was filtered. The filtrate was evaporated under reduced pressure and a brown oil was obtained as residue. Its hexane spectrum showed two strong absorptions at 2007 and 1965 cm, which are due to the stretching vibrations of the terminal CO groups, and an absorption at 1158 cm, which is due to the stretching vibration the CS group is declining.

It was not possible to isolate the thioeailxmy! Complex CcHeFe (CQ) ₂ -CSHHCH, but after treatment with HCl the starting thiocarbonyl complex was obtained.

Example 6

At room temperature, 1 mmol of KCITS was added to a solution of CCcHcFe (CO) ₂ CS] PFg in 20 ml of dry acetone. The resulting mixture was stirred for 1 hour _β The solvent was evaporated under vacuum to give a red pike stand, which was dissolved in GHCl .. and filtered, and then the resulting solution was reduced to 10 ml dried. The addition of pentene gave a low yield (20 %)

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Example 7 f

Production of

A suspension of 1 g of [C ₅ H ₅ Fe (CO) ₂ C ₂ H ₄ ] BF ₄ in 50 ml of anhydrous methyl alcohol was stirred for about 7 hours with an excess of Na ₂ GO ₅ at room temperature and under a nitrogen atmosphere. The obtained solution was filtered and the solvent was removed under reduced pressure. The obtained solid compound was treated with dichloromethane and dried again. An oil was obtained which sublimed under vacuum (2 mm Hg) while the product obtained was cooled to -78 ° C. The yield was 70 %. The elemental analysis provided the following values:

ber .: C 50, 5.09 found : 51, 5.04 Example 8 Manufacturing from i (CO) ₂ CH ₂ CH ₂ NHR 9 H. 8th C ₅ H ₅ Fc

At room temperature, the appropriate amine was added to a suspension of Λ g [C ₅ H ₅ Fe (CO) ₂ C ₂ H ^] BF ₄ in 100 ml of ether. After about 2 hours the solution was filtered and the solvent was evaporated under reduced pressure. The oil obtained was purified by sublimation according to the method described above. The yield was 60% <. The complex decomposed rapidly in air, it was identified by its IR spectrum, which had two absorption bands at 1950 and 2004 cm, which are typical for the / class of complexes and the stretching frequencies of the carboxyl groups are due.

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Example 9

Preparation of [C ₅ H ₅ Fe (CO) ₂ OH ₂ -CHOCH-IBF ^

_{The complex C 5} H ₅ Fe- (CO) ₂ CH ₂ CH ₂ OCH, dissolved in anhydrous tetrahydrofuran, was treated with the stoichiometric amount of CiLBF ^. After about 1 hour, the solvent was evaporated and the solid compound treated again with acetone was precipitated by adding ethyl ether. The yield was 60 %.

* Example 10

The olefin complex [C ₅ H ₅ Fe (CO) ₂ CH ₂ CH ₂ OCHa] BF ^ in tetrahydrofuran was irradiated for about 1 hour by means of a UV lamp of the Hanovia type (400 watts), an almost quantitative yield of the dimer [ C ₅ H ₅ Fe (CO) ₂ ] ₂ received »

The olefin complex [C5H ₅ Fe (CO) ₂ CH ₂ CH ₂ OCH ₅ ] " ¹ " was treated with ethylene at 40 atmospheres at 80 ° C. in an autoclave for three hours. In addition to the dimer [C ₅ H ₅ Fe (CO) ₂ ] ₂ , the complex [C ₅ H ₅ Fe (CO) ₂ CH ₂ CH ₂ ] ^{+ was obtained} in a low yield.

Example 11

A solution of 0.065 g (1 mmol) NaN in 3 ml Waiser was mixed with stirring to a solution of 0.584 g (1 mmol) [O ₅ H ₅ Fe- (CO) ₂ P (OgH ₅ ),] PFg in 50 ml Acetone added. After stirring for 4 hours at room temperature, the solvent was removed using a rotary evaporator and the residue was dissolved in dichloromethane. The solution was then ebromatographed over aluminum oxide using dichloromethane as the eluent. Man. received a red solution

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which the complex C ₅ HeFe (OO) P (CgHe) X (HCO) was precipitated by pentane. The yield was 66%. The complex was red and had a melting point of 130 to 13I ⁰ C. Elemental analysis gave the following Verte: calc .: C 66.20 H 3.09 H from 4.4 to 3 gef.i 65.50 4.52 3 20th

Example 12

A suspension of 0.584 g (1 mlol) [CcH ₅ Fe (CO) ₂ P (CgH ₅ ) J] -PFg in 50 ml dichloromethane was mixed with 0.10 ml (2 mlol) NHg-NH ₂ at room temperature with stirring and under implemented in a nitrogen atmosphere. The reaction mixture immediately turned red and after about 1 hour it was filtered. The solvent was removed from the resulting solution by evaporation in vacuo and the residue was dissolved in the minimal amount of thick chloromethane. By adding pentane, the complex O ₅ H ₅ Fe (CO) ^ NCO was obtained in a yield of 56 #.

Example 13

A suspension of 0.584 g (1 mllol) IGJiJe (GO) ^ B (G ₆ EJJ ¹⁹ S in 50 ml dichloromethane was reacted with NHJRHCHs in a slight stoichiometric excess at room temperature, with stirring and under a nitrogen atmosphere. The reaction Raise Hung immediately became red and after about 1 hour it was filtered, the solvent was removed from the resulting solution by evaporation in vacuo and the residue was dissolved in the minimum amount of dichloromethane. Addition of pentane gave the complex CcHeFe (CO) ₂ NCO in 37 yield % ·

Patent claims:

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Claims (1)

aer. Patent claims 1. Process for the production of special iron complexes,
characterized! that you are a nucleophilic agent
is reacted with a cationic iron complex OCE general formula in the L a ligand, which both from a saturated compound from the group phosphine, areine or derivatives
thereof, as well as from an unsaturated compound from the group OS, 0H ₂ »0H ₂ or OH ^ GHR, * where H is an alkyl or
Is aryl radical, and Y "means a negative ion from the group BF" * ", Cl"", B (OgHc) ^", 2. The method according to claim 1, characterized in that the ligand L 08 means = 3. The method of claim 1, characterized in that the ligand L _s · ethylene means 4 «A method according to claim i, characterized in that the ligand L _s triphenylphosphine means. 5. Verfahren.nach claim 1, characterized in that the nucleophile N, "" H H ₂ ^ H ₃ H ₅ H, BHgfi, NHRR * Cf "NCO *", NCS "j * CN"" , RCOO "", in which H and R 'denote alkyl or aryl radicals, is used. 'consists 1098 * 4/1944 6o method according to any one of the preceding claims, characterized in that the reaction at a temperature is carried out within the range of 20 to 60 ° 0, preferably at room temperature. 7. The method according to any one of the preceding claims, characterized in that the reaction is in the presence an inert solvent from the group consisting of tetrahydrofuran, dichloromethane or ethyl ether. 8. The method according to any one of claims 1 to 6, characterized characterized in that the reaction is carried out in the presence of only the nucleophilic agent acting as ale solvent will. 9. A process for the preparation of TT-olefinic iron complexes, characterized in that an iron complex the formula CO in which X is a nucleophile as defined in claim 5 Agent means n with a carbanion compound of the formula is implemented in which R and Y "" are one of those specified in the preceding claims Has meanings. 10. The method according to claim 9 _f, characterized in that the reaction is carried out at tree temperature. 11. The method according to claims 9 and 10, characterized in that that the reaction in the presence of an inert solvent 109844/1944 211622 $ solvent from the tetrahydrofuran, dichloromethane group and ethyl ether is carried out. 12. A process for the preparation of vinyl compounds, characterized in that a T-olefinic iron complex the general formula "^ NJO in the Z and Y - those in one of the preceding claims have given meanings, is exposed to thermal radiation or light radiation. 13. A process for the preparation of vinyl compounds, characterized in that a TT ^ -olefinic iron complex the general formula G ₅ H ₅ F GO CO in which X and T "" are those in one of the preceding claims Have given meanings, with ethylene under pressure and at a temperature within the range of 60 up to 90 ° C is implemented. 14. Products and processes as described in the description and are described in the examples. 109844/1944