US 4,625,069 A · Fluorochemical rhodium compounds

Abstract

Coordination compounds of rhodium are solid salts having donor ligands of [(aryl).sub.3 P].sub.3 Rh.sup.+ and a non-coordinated counterion derived from a fluorochemical acid, the salts having the formula: [(aryl).sub.3 P].sub.3 Rh.sup.+ (counterion).sup.-. The salts are prepared by reacting [(aryl).sub.3 P].sub.4 RhH, which is and uncharged rhodium hydride, with a fluorochemical acid selected form acids having the formulae: HC(R)(SO.sub.2 R.sub.f).sub.2, R.sub.f 'SO.sub.3 H, and HN(SO.sub.2 R.sub.f).sub.2 wherein R.sub.f and R.sub.f ' are perfluoroalkyl groups and R is lower alkyl substituted or unsubstituted phenyl, hydrogen, Cl, SO.sub.2 R.sub.f or R.sub.f. Carbonylation of the [(aryl).sub.3 P].sub.3 Rh.sup.+ (counterion).sup.- compounds of this invention, e.g., by contacting the salts of the invention with carbon monoxide gas, produces salts having the formula: [(aryl).sub.3 P].sub.3 Rh(CO).sub.n.sup.+(counterion).sup.-, wherein n is 1 or 2, and (counterion).sup.- is as defined above. These carbonylated derivatives as well as the above-described precursor salts are useful as catalysts in organic transformation reactions, such as isomerization, cyclization and hydroformylation reactions.

Claims12

Dependent claims

In a process for olefin isomerization comprising the steps of:

reacting an olefin compound having at least one carbon-to-carbon double bound in the presence of a catalytically effective amount of a coordination compound of rhodium, optionally in the presence of heat, and recovering the resulting isomerized olefin product,
the improvement comprising using as said catalyst a rhodium coordination compound having the formula:
[(aryl).sub.3 P].sub.3 Rh.sup.+ (counterion).sup.- or
[(aryl).sub.3 P].sub.3 Rh(CO).sub.n.sup.+ (counterion).sup.-
wherein
aryl is phenyl, phenyl substituted by 1 to 3 methyl groups, or for one aryl group, polystyryl,
n is the integer 1 or 2,
(counterion).sup.- is the conjugate base of acids selected from HC(R)(SO.sub.2 R.sub.f).sub.2, R.sub.f 'SO.sub.3 H, and HN(SO.sub.2 R.sub.f).sub.2
wherein
R.sub.f is a perfluoroalkyl group having 1 to 20 carbon atoms,
R.sub.f ' is a perfluoroalkyl group having 4 to 20 carbon atoms, and
R is lower alkyl, phenyl, Cl, H, SO.sub.2 R.sub.f, or R.sub.f.

9 more elements

In a process for hydroformylation of an olefin compound comprising the steps of:

reacting an olefin having at least one carbon-to-carbon double bond and a mixture of hydrogen and carbon monoxide, in the presence of a catalytically effective amount of a coordination compound of rhodium, heating the resulting mixture, and recovering the resulting aldehyde product,
the improvement comprising using as said catalyst a rhodium coordination compound having the formula:
[(aryl).sub.3 P].sub.3 Rh.sup.+ (counterion).sup.- or
[(aryl).sub.3 P].sub.3 Rh(CO).sub.n.sup.+ (counterion).sup.-
wherein
aryl is phenyl, phenyl substituted by 1 to 3 methyl groups, or for one aryl group, polystyryl,
n is the integer 1 or 2,
(counterion).sup.- is the conjugate base of acids selected from HC(R)(SO.sub.2 R.sub.f ').sub.2, R.sub.f SO.sub.3 H, and HN(SO.sub.2 R.sub.f).sub.2
wherein
R.sub.f is a perfluoroalkyl group having 1 to 20 carbon atoms,
R.sub.f ' is a perfluoroalkyl group having 4 to 20 carbon atoms, and
R is lower alkyl, phenyl, Cl, H, SO.sub.2 R.sub.f, or R.sub.f.

9 more elements

In a process for the cyclotrimerization of alkynes comprising of steps of:

reacting an alkyne having at least one carbon-to-carbon triple bond, in the presence of a catalytically effective amount of a coordination compound of rhodium, heating the resulting mixture, and recovering the resulting cyclic trimer,
the improvement comprising using as said catalyst a coordination rhodium compound having the formula:
[(aryl).sub.3 P].sub.3 Rh.sup.+ (counterion).sup.- or
[(aryl).sub.3 P].sub.3 Rh(CO).sub.n.sup.+ (counterion).sup.-
wherein
aryl is phenyl, phenyl substituted by 1 to 3 methyl groups, or for one aryl group, polystyryl,
n is the integer 1 or 2,
(counterion).sup.- is the conjugate base of acids selected from HC(R)(SO.sub.2 R.sub.f).sub.2, R.sub.f 'SO.sub.3 H, and HN(SO.sub.2 R.sub.f).sub.2
wherein
R.sub.f is a perfluoroalkyl group having 1 to 20 carbon atoms,
R.sub.f ' is a perfluoroalkyl group having 4 to 20 carbon atoms, and
R is lower alkyl, phenyl, Cl, H, SO.sub.2 R.sub.f, or R.sub.f.

9 more elements

Dependencies are inferred from the claim text.

Fluorochemical rhodium compounds

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Fluorochemical rhodium compounds

Life of this patent

Abstract

Claims12