Polymer-bound cyclopentadiene metal carbonyl compounds and their ligand substitution derivatives
AssigneeHans H. Brintzinger
InventorsManfred Boldt, Giuseppe Gubitosa, Hans H. Brintzinger, Ferdinand Wild
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Abstract
Polymeric catalysts containing groups of the general formula: [--(C.sub.5 R.sub.4)Me(CO).sub.x L.sub.y ].sub.z, wherein (C.sub.5 R.sub.4) is a sustituted or unsubstituted cyclopentadiene group; Me is a transition metal; and L is alkyl or aryl phosphine, alkyl phosphite, nitrosyl, allyl, SnCl.sub.3, halogen or hydrogen. Such groups are bound to polymeric carriers such as polystyrene-based copolymers, silica gel or silicate glass. Processes for preparing such catalysts and methods for their use are also disclosed.
Claims28
Polymer-bound cyclopentadiene metal carbonyl compounds and the ligand substitution derivatives thereof characterized in that said compounds and derivatives contain groups of the general formula
- [--(C.sub.5 R.sub.4)Me(CO).sub.x L.sub.y ].sub.z
- in which
- R is a hydrogen atom, a C.sub.1-4 -alkyl group, a benzene group or a diphenylmethyl group,
- Me is a transitional metal from the 6th, 7th, or 8th transitional group of the periodic table,
- x is 1, 2, or 3,
- L is a tri(C.sub.1-3 -Alkyl) phosphine group, a triphenylphosphine group, a tri(C.sub.1-3 -alkyl)-phosphite group, a nitrosyl group, an allyl group, a SnCl.sub.3 group, a halogen atom, or a hydrogen atom,
- y is 0, 1 or 2, and
- z is 1, 2, 3, or 4,
- wherein said groups are covalently bound to a polymer carrier by way of methylene groups, Di(C.sub.1-3 -alkyl)-methylene groups, (C.sub.1-3 -alkyl)-phenyl methylene groups, diphenyl methylene groups, (C.sub.2-4 -alkylene) groups, Di(C.sub.1-3 -alkyl)-silyl groups, Di(C.sub.1-3 -alkoxy)-silyl groups, diphenyl silyl groups, (C.sub.1-3 -alkyl)-chlorine-silyl groups, phenyl chlorine silyl groups, dichlorine silyl groups, or by way of analogous silyl groups substituted with two or three groups of the general formula --(C.sub.5 R.sub.4)Me(CO).sub.x L.sub.y.
A catalyst having a structure selected from the group consisting of ##STR5## wherein R is an alkyl group containing 1 to 4 carbon atoms, and P represents a polystyrene polymer.
A method of preparing a catalyst of the formula ##STR6## wherein R is an alkyl group containing from 1 to 4 carbon atoms and P is a polystyrene polymer backbone, under an inert atmosphere, comprising,
- (a) dissolving a compound having the structure ##STR7## in a suitable solvent, wherein P and R have the meaning described above, and reacting with
- (b) an alkyl organolithium material containing from 1-4 carbon atoms, continuing agitation for a period of time sufficient to effect reaction;
- (c) filtering the polymer from solution, readding to a suitable solvent, and adding [Rh(CO).sub.2 X].sub.2 wherein X is a halogen;
- and
- (d) continuing stirring for a sufficient time to effect reaction, then removing the catalyst from solution extracting with a suitable solvent, and drying prior to use.
A method of preparing a catalyst of the formula ##STR8## wherein P is a polystyrene polymer backbone, comprising, under an inert atmosphere;
- (a) dissolving a polymer having the general formula;
- ##STR9## in a suitable solvent and adding an alkyl organolithium compound, stirring for sufficient time to effect reaction, filtering the polymer from solution and washing with a suitable solvent before refiltering to yield a polymer having the general formula;
- ##STR10## (b) then adding recovered polymer to a suitable solvent and adding sufficient [Rh(CO).sub.2 X].sub.2, wherein X is a halogen to provide the desired percentage of rhodium and agitating the mixture for sufficient time to effort reaction;
- (c) recovering the polymer, washing with a suitable solvent, and drying to yield a polymeric catalyst having the structure;
- ##STR11##
Dependencies are inferred from the claim text.