Process for preparing hydridocarbonyltris(triphenylphosphine)rhodium(I)

Patent metadata

Field	Value
Publication number	US-9834572-B2
Application number	US-201515324017-A
Country	US
Kind code	B2
Filing date	Jul 3, 2015
Priority date	Jul 11, 2014
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

The present invention relates to a process for preparing hydridocarbonyltris(triphenylphosphine)rhodium(I), RhH(CO)(PPh 3 ) 3 , also referred to hereinafter as “Rh-hydrido.” An alcoholic suspension of triphenylphosphine is stirred with an Rh(III) chloride precursor at elevated temperature. The Rh(III) chloride precursor used may be rhodium(III) chloride hydrate RhCl 3 *xH 2 O or rhodium(III) chloride solution H 3 [RhCl 6 ]*(H 2 O) n . After cooling, alcoholic alkali metal hydroxide solution is added, and the mixture is stirred for a few hours. Finally, sparging is effected with CO gas and the Rh-hydrido formed is removed. Rh-hydrido can be prepared by this process on the industrial scale with high yields and at very good quality.

First claim

The invention claimed is:

1. A one-step process for preparing RhH(CO)(PPh 3 ) 3 , comprising these steps:
(a) Preparing an alcoholic suspension of triphenylphosphine PPh 3 in an inerted reaction vessel,
(b) Mixing the alcoholic PPh3 suspension with an Rh(III) chloride precursor at a temperature of 30 to 40° C.,
(c) Stirring the reaction mixture of PPh 3 suspension and Rh(III) chloride precursor at an elevated temperature,
wherein stirring is carried out with reflux if the boiling point of the alcohol is below 85° C., or
wherein stirring is carried out with the reaction vessel having an internal temperature of 75° C. to 85° C. if the boiling point of the alcohol is 85° C. or higher,

(d) Cooling the suspension from step (c) down to 35-50° C.,
(e) Adding an alcoholic alkali hydroxide solution,
(f) Stirring the reaction suspension at 35-50° C.,
(g) Sparging with CO gas,
(h) Separating and optionally washing and drying the hydridocarbonyltris(triphenylphosphine)rhodium(I) complex, RhH(CO)(PPh 3 ) 3 .

2. The process according to claim 1 , wherein the Cooling of the suspension from step (c) down to 40-50° C., and the Stirring the reaction suspension at 40-50° C.

3. The process according to claim 1 , wherein the Rh(III) chloride precursor being selected from rhodium(III) chloride hydrate, RhCl 3 *xH 2 O, rhodium(III) chloride solution H 3 [RhCl 6 ]*(H 2 O) n , aqueous or alcoholic solutions of RhCl 3 *xH 2 O or H 3 [RhCl 6 ]*(H 2 O) n or mixtures thereof.

4. The process according to claim 2 , wherein the alcohol for preparing alcoholic solutions of RhCl 3 *xH 2 O and H 3 [RhCl 6 ]*(H 2 O) n and also mixtures of aqueous and alcoholic solutions of RhCl 3 *xH 2 O and H 3 [RhCl 6 ]*(H 2 O) n is selected from the group consisting of methanol, ethanol, n-propanol, 2-propanol and mixtures thereof.

5. The process according to claim 1 , wherein the alcohol for preparing the solutions of PPh 3 and the alkali hydroxide solution is selected from the group consisting of methanol, ethanol, n-propanol, 2-propanol and mixtures thereof.

6. The process according to claim 1 , wherein the alkali hydroxide is potassium hydroxide.

7. The process according to claim 1 , wherein the PPh 3 suspension and the Rh(III) chloride precursor solution are mixed discontinuously in accordance with step (b), wherein the Rh(III) chloride precursor solution is added to the PPh 3 suspension already present.

8. The process according to claim 1 , wherein sparging with CO gas is carried out at standard pressure.

9. The process according to claim 1 , wherein step (c), the stirring of the reaction mixture of PPh 3 suspension and Rh(III) chloride precursor at an elevated temperature, is carried out for a period of 1.5 to 3 hours.

10. The process according to claim 1 , wherein step (f), the stirring of the reaction suspension, is carried out for a period of 1.5 to 3 hours at a temperature of 40-50° C.

11. The process according to claim 1 , wherein step (g), sparging with CO gas, is carried out for a period of 2 to 16 hours.

12. The process according to claim 1 , wherein in step (h), the end product, RhH(CO)(PPh 3 ) 3 , is washed with an alcohol, water or a combination thereof.

13. The process according to claim 1 , wherein the alcohol for preparing the alcoholic suspension of triphenylphosphine PPh 3 is selected from the group consisting of methanol, ethanol, n-propanol, 2-propanol and mixtures thereof.

Assignees

• Umicore Ag & Co Kg

Inventors

• Doppiu Angelino
• Karch Ralf
• Rivas-Nass Andreas
• Woerner Eileen

Classifications

• C07F15/008 Primary

  without a metal-carbon linkage · CPC title

• C07F15/0073 Primary

  Rhodium compounds · CPC title