Monomeric, polymeric and carrier-fixed rhodium complex compounds, process for their production and their use as catalysts
AssigneeDeutsche Gold- und Silber-Scheideanstalt vormals Roessler
InventorsPeter Panster, Wolfgang Buder, Peter Kleinschmit
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Abstract
The invention relates to coordination compounds of rhodium with silicon-substitued dialkyl or diaryl sulfide groups as ligands in monomeric, polymeric or carrier-fixed forms. The substance can be used as catalysts.
Claims32
A complex compound of rhodium, comprised of at least one sulfide of the general formula (1)
- R.sub.3-x.sup.1 (R.sup.2 O).sub.x Si--R.sup.3 --S--R.sup.4 --Si(OR.sup.5).sub.y R.sub.3-y.sup.6 ( 1)
- coordinatively bound to the central atom, any free valencies are occupied by carbon monoxide, an olefin, amine, phosphine or nitrile and a required charge equalization is accomplished with chloride, bromide or iodide ion, an acetate, trifluoroacetate or trifluoro-propionate ion, complete or partial substitution of such anions by hydride ion, being optional whereby in formula (1)
- each of R.sup.1 and R.sup.6 is a straight-chain alkyl or branched alkyl with 1 to 5 C-atoms, a cyclo-alkyl with 5 to 8 C-atoms, benzyl or phenyl, or substituted benzyl or substituted phenyl with methyl, ethyl, propyl, methoxy, ethoxy, NO.sub.2, halide or cyanide;
- chloride or bromide;
- R.sup.2 and R.sup.5 each is a straight-chain alkyl or branched alkyl with 1 to 5 C-atoms, cycloalkyl with 5 to 8 C-atoms, substituted or unsubstituted phenyl or benzyl group or the 2-methoxy or 2-ethoxy-ethyl group, whereby R.sup.2 and R.sup.5 have the same or a different meaning;
- R.sup.3 and R.sup.4 each is a straight-chain alkylene or branched alkylene with 1 to 10 C-atoms a phenylene or cycloalkylene group with 5 to 8 C-atoms, unsubstituted or substituted with a methyl, ethyl, propyl or iso-propyl;
- or a unit of the formula ##STR9## whereby n or m may be a number from 0 to 5 and H atoms in ring position may be substituted partly by halide, F, Cl, Br, or the cyanide group, and R.sup.3 and R.sup.4 have the same or a different meaning and
- whereby x and y may be 1, 2 or 3;
- but also 0, whenever R.sup.1 R.sup.6 is equal to chlorine or bromine, and x and y have the same or a different meaning.
A polymer which is slightly soluble in organic solvents, with a silicic acid-like structure and the function of a rhodium carrier, to which rhodium salts of a halogen acid, or of a lower organic carboxylic acid, containing carbon monoxide, olefine, amine, phosphine or nitrile ligands or crystal water, are coordinatively bound by way of at least one ligand L.sup.1,
- whereby L.sup.1 signifies a sulfide compound L with trifunctionally substituted silicon of the formula:
- R.sub.3-x.sup.1 (R.sup.2 O).sub.x Si--R.sup.3 --S--R.sup.4 --Si(OR.sup.5).sub.y R.sub.3-y.sup.6
- in which the rhodium:
- sulfide ratio ranges from 1:1 to 1:10.sup.6,
- obtained from complex compounds of the stoichiometric compound RhX.sub.3 L.sub.3 in which L represents at least one ligand of the formula (1) and carbon monoxide, olefine, amine, phosphine or nitrile or crystal water bound to any free coordination places and X, is chloride, bromide, iodide, acetate, trifluorocetate, or trifluoropropionate,
- are reacted with water or an aqueous acid solution while distilling off of developing alcohol, or phenol.
A polymer which is slightly soluble in organic solvents, with a silicic acid-like structure and the function of a rhodium carrier, to which rhodium salts of a halogen acid, or of a lower organic carboxylic acid, containing carbon monoxide, olefine, amine, phosphine or nitrile ligands or crystal water, are coordinatively bound by way of at least one ligand L.sup.1.
- whereby L.sup.1 signifies a sulfide compound L with trifunctionally substituted silicon of the formula:
- (1)
- R.sub.3-x.sup.1 (R.sup.2 O).sub.x Si--R.sup.3 --S--R.sup.4 --Si(OR.sup.5).sub.y R.sub.3-y.sup.6
- in which the groups OR.sup.2, OR.sup.5, R.sup.1 and R.sup.6, present originally, are at least partially split off hydrolytically as alcohol, phenol, HCl or HBr,
- and in which the rhodium:sulfide ratio ranges from 1:1 to 1:10.sup.6,
- obtained by reacting the ligand L of the formula (1) with carbon monoxide, olefine, amine, phosphine or nitrile, or crystal water to any free coordination places,
- with water or an aqueous acid solution while distilling off of developing alcohol or phenol,
- and the solid matter formed is reacted with rhodium compounds, in the form of aqueous or anhydrous salts of a halogen acid or of a lower carboxylic acid, or in the form of rhodium compounds containing easily displaceable ligands, or with the compound [Rh(CO).sub.2 Cl].sub.2.
A process for the production of a polymer as defined in claim 34, wherein at least one ligand of the formula (1), provided with trifunctionally substituted silicon and carbon monoxide, olefine, amine, phosphine or nitrile or crystal water, bound to still possibly free coordination places, and X is chloride, bromide, iodide, acetate, trifluoroacetate or trifluoropriopionate is reacted with water or an aqueous acid solution while distilling off of developing alcohol or phenol,
- and the solid matter formed thereby is reacted with rhodium compounds in the form of aqueous or anhydrous salts of a halogen acid or of a lower carboxylic acid, or rhodium compounds carrying easily displaceable ligands, or with the compound [Rh(CO).sub.2 Cl].sub.2.
A rhodium complex compound bound by way of inorganic carriers, and showing surface-positioned oxygen atoms having the formula:
- RhX.sub.3 L.sub.3 or RhCl(CO)L.sub.2,
- wherein X is chloride, bromide, iodide, acetate, trifluoroacetate or trifluoropropionate and
- L represents at least one ligand of the formula (1)
- R.sub.d-x.sup.1 (R.sup.2 O).sub.x Si--R.sup.3 --S--R.sup.4 --Si(OR.sup.5).sub.y R.sub.3-y.sup.6
- and carbon monoxide, olefin, amine, phosphine or nitrile, or crystal water bound to any free coordination places, the bond to the carrier is established by reaction of the acid hydrogen with the OR.sup.2, OR.sup.5, R.sup.1 and R.sup.2 groups present, while alcohol, phenol, HCl or HBr is distilled off, wherein any uncoordinated radicals of the sulfide are bound on the carrier and the rhodium:
- sulfide ratio ranges from 1:1 to 1:10.sup.3 ;
- said rhodium complex being obtained from a solution of the compound RhX.sub.3 L.sub.3 or RhCl(CO)L.sub.2, which is treated within the scope of the quantitative limit ratios provided with a suspension of the carrier material in an inert organic solvent at temperatures between room temperature and the reflux temperature of the suspension agent used.
A rhodium complex compound bound by way of inorganic carriers, and showing surface-positioned oxygen atoms having the formula:
- RhX.sub.3 L.sub.3 or RhCl(CO)L.sub.2,
- wherein X is chloride, bromide, iodide, acetate, trifluoroacetate or trifluoropropionate and
- L represents at least one ligand of the formula (1)
- R.sub.3-x.sup.1 (R.sup.2 O).sub.x Si--R.sup.3 --S--R.sup.4 --Si(OR.sup.5).sub.y R.sub.3-y.sup.6
- and carbon monoxide, olefin, amine, phosphine or nitrile, or crystal water bound to any free coordination places, the bond to the carrier is established by reaction of the acid hydrogen with the OR.sup.2, OR.sup.5, R.sup.1 and R.sup.6 groups present, while alcohol, phenol, HCl or HBr is distilled off, wherein any uncoordinated radicals of the sulfide are bound on the carrier and the rhodium:sulfide ratio ranges from 1:1 to 1:10.sup.3 ;
- said rhodium complex being obtained by treating a sulfide of the formula (1) with a suspension of the carrier material in an inert organic solvent at the stated temperature conditions, and subsequently the solid substance formed thereby is reacted with rhodium compounds carrying easily displaceable ligands, and in the form of anhydrous or aqueous salts of a halogen acid or of a lower carboxylic acid, or with the compound [Rh(CO).sub.2 Cl].sub.2.
Dependencies are inferred from the claim text.