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  Immobilized metal complex catalysts, process for preparation thereof and use thereofUSPTO Application #: 20060135356Title: Immobilized metal complex catalysts, process for preparation thereof and use thereof Abstract: wherein M is a Group VIII metal, Lx is a phosphine ligand, n is an integer with a value between 2 and 6, MLx is an organometallic complex. The present invention provides a novel immobilized metal complex catalyst of Formula I (end of abstract) Agent: Nixon & Vanderhye, PC - Arlington, VA, US Inventors: Raghunath Vitthal Chaudhari, Bibhas Ranjan Sarkar, Kausik Mukhopadhyay USPTO Applicaton #: 20060135356 - Class: 502167000 (USPTO) Related Patent Categories: Catalyst, Solid Sorbent, Or Support Therefor: Product Or Process Of Making, Catalyst Or Precursor Therefor, Organic Compound Containing, Organic Phosphorus Or Nitrogen, Except The Ammonium Ion, Organic Nitrogen Containing The Patent Description & Claims data below is from USPTO Patent Application 20060135356. Brief Patent Description - Full Patent Description - Patent Application Claims
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a division of application Ser. No. 10/731,446, filed Dec. 10, 2003, now pending; the entire contents of which is hereby incorporated by reference in this application. FIELD OF THE INVENTION [0002] The present invention relates to a novel immobilized metal complex catalyst of the Formula I wherein M is a Group VIII metal, n is an integer with a value between 2 and 6, ML.sub.x is an organometallic complex. [0003] The present invention also provides a process for the preparation of a novel immobilized metal complex catalyst and use thereof for carbonization reactions. More particularly the present invention relates to the preparation of immobilized transition metal complex catalyst having a general representation as in Formula I above, wherein the organometallic complex ML.sub.x is anchored to the internal surface of the solid matrix by an anchoring agent of Formula VI wherein Z is a functional group as --NH.sub.2, --SH, vinyl, allyl etc., "n" may have integral values between 2 and 6, "m" may have integral values between 1 and 3. [0004] The catalysts thus prepared are solid, robust and heterogeneous and hence, separable from the reaction mixture by simple filtration techniques and are therefore recyclable catalysts for carbonylation of aryl-olefins, alcohols, substituted alkyl halides etc., optionally in presence of an alkali metal halide and organic acid as promoters. Specifically, the hydroxycarbonylation of the aryl-olefins and alcohols yields selectively the branched carboxylic acids, which are representatives of a class of non-steroidal anti-inflammatory drugs. These easy separable catalysts along with their higher performance in comparison to those in the existing art, with respect to those in the existing art, with respect to the resolvability and the leaching of the metal into the reaction mixture, mark the adorable advantages of the invention. BACKGROUND OF THE INVENTION [0005] Aryl and aliphatic carboxylic acids have a variety a variety of applications in industries as anti-inflammatory drugs, fine chemicals, etc. the prior art describes the catalyst systems for employment in the processes for the preparation of carboxylic acids using the carbonization reaction on a variety of substrates. So for the most preferred catalyst system has been the homogeneous transition metal catalysts, typically palladium complexes. Generally, the various catalyst systems used for the hydrocarboxylation of olefins and comprises of a palladium source, a phosphine ligand, and a hydrogen halide promoter. Reference can made of Bittler et al. (Angew. Chem. Int. Eng. Ed., 7, 1968, 329), who described the hydrocarboxylation of olefins using a catalyst system comprising of palladium source as PdCl.sub.2 or PdCl.sub.2 (PPh.sub.3).sub.2, a ligand as triphenylphosphine (PPh.sub.3) and HCl, has been found to occur only under drastic conditions such as 300 to 700 atm of carbon monoxide pressure. Oi et al. (J. Mol. Catal. A: Chem., 115, 1997, 289) have reported hydroesterification of styrene using cationic palladium complexes which proceeds under mild reaction conditions (20) atm, 80.degree. C.) to give 91 to 94% product yield four hours (TOF.about.11 h.sup.-1) with a n:iso ratio of 60: recently Seayad et al. (Ind. Eng. Chem Res., 37, 1998, 2180) have a catalyst system consisting of Pd(Oac).sub.2, excess PPh.sub.3 and p-toluenesulphonic acid (TsOH), with a n:iso ratio of 35:65 even though various palladium phosphine complexes with N-containing ligands had not been used by then. The drawbacks for these catalyst systems lie in the law yield and reaction rates along with the drastic operating conditions. Thus it was necessary to search for a better process wherein the yield, selectivity are good using milder operating milder operating conditions. [0006] Reference is made to U.S. Pat. No. 6,069,253, wherein Chaudhari et al. have described the preparation of metal complexes containing a semilabile anionic ligand, which is a chelating organic compound containing an N donor and a O.sup.- group. Their appropriate use as catalysts for the preparation of the saturated carboxylic acids and esters by the hydrocarboxylation of the olefinically unsaturated compounds has been described in full in U.S. Pat. No. 6,294,687 by the same authors. Describes the process describes the use of a metal complex catalyst with a N--O chelating ligand, a protonic acid and an alkali-metal halide as promoters, in presence or absence of an 120.degree. C. for a reaction period of 30 to 180 minutes under a total pressure of 1 to 40 atmospheres, gained the system major advantages. The high turnover frequencies (.about.2600 h.sup.-1) observed along with the height selectivity of >98% of the desired iso-product are some of the distinguishing features of the system. However, being a homogeneous catalyst, the system suffered from major drawback of catalyst-product separation and proper recycle, obviating the need for recyclable heterogeneous catalysts. [0007] An important method for hydrogenising homogeneous catalysts is the application of two-phase systems comprising an aqueous phase containing water-soluble organometallic catalysts and a water immiscible phase (E. G. Kuntz, CHEMTECH, 17, 1987, 540; EP 0107006; B. Cornils, W. A. Herrmann (Eds.), Aqueous phase Organometallic Catalysis, Wiley--VCH, 1998, Weinheim). Reference can be made to recent publications (Chem. Commun. 2000, 1239; J. Mol. Catal. A; Chem, 181 (1-2), 2002, 221), where a novel water-soluble palladium complex catalyst has been proposed for the hydrocarboxylation of olefins giving high selectivity (>98%) to the iso-product. The drawback of this system however was the much lower reaction rates (TOF.about.280 h.sup.-1 in comparison of the homogeneous counterpart. [0008] Supported aqueous phase catalysis (SAPC) is another method for the heterogenization of homogeneous catalysts, wherein in water-soluble catalyst martial is contained in the thin film of water adhered to the surface of a high surface area inorganic solid support (U.S. Pat. No. 5,736,980 and U.S. Pat. No. 5,935,892). Reference is made to U.S. Patent Publication 2002-0137964, wherein Jayasree Seayad et al. have described a process for the preparation of saturated carboxylic acid esters using a novel supported aqueous catalyst by carbonylation reaction. The drawbacks are, very low yields (.about.20%) and selectivity to the desired iso-product (.about.55-60%). [0009] Various other reports attempted the use of supported catalysts for carbonylation reactions. Reference can be made of Wu (U.S. Pat. No. 5,135,026), wherein palladium/copper catalyst support on Montmorillonite KSF, was used for carbonylation of 4-isobutylstyrene in presence of (+)-neomethyldiphenylphosphine as a ligand and Tetrahydrofuran as solvent at 100.degree. C., 300 psig of carbon monoxide pressure for .about.92 hours, producing good selectivity (.about.97%) to the desired product. Other variations regarding the different cyclic ligands have been discussed in the same. Another relevant reference is Tanielyan et al. (U.S. Pat. No. 6,025,295), wherein various supported palladium complexes have been reported to exhibit catalytic property towards carbonization reactions. The main drawbacks of most of the reports are the poor conversion, turnover frequency and selectivity. The stability of the catalysts is also a major issue in all of these cases. OBJECTS OF THE INVENTION [0010] The main object of the present invention is to provide a process for the preparation of novel immobilized metal complex catalysts and use thereof for carbonylation reactions by anchoring in solid matrices and thereafter, their uses as novel heterogeneous catalysts for carbonylation reactions, which obviates the drawbacks as detailed above. [0011] Another object of this invention is to provide a novel process for the immobilization of the metal complexes inside the porous matrices, essentially the microporous and mesoporous matrices, whereby the transition metal complex being covalently or coordinatively bonded to the interior surface of matrices only, thus with decreased mobility are trapped, hence allowing only insignificant leaching or no leaching of the metal complexes into the reaction mixture under the carbonylation reaction conditions. [0012] Still another object of the invention is to provide an efficient process for the preparation of the saturated carboxylic acids by carboxylic acid by carbonylation reaction using the aforesaid catalysts under mild operating conditions. [0013] Yet another object of the invention is to demonstrate the use of alkali metal halide and any Bronsted acid, specifically organic sulphonic acid in the preparation of the saturated carboxylic acids, with a selectivity constraint of 95% to the desired product. [0014] Still another object of the invention is to demonstrate the economic usage of catalysts through proper recycles. These catalysts being highly stable, and non-leaching, and hence show excellent recyclability. Even if these heterogeneous catalysts may have lower turnover frequency per batch in comparison to the homogeneous counterparts, the cumulative turnover numbers after the repeated recycles add to value of the process, and hence process economy. SUMMARY OF THE INVENTION [0015] Accordingly the present invention relates to an immobilized metal complex catalyst of the Formula I wherein M is a Group VIII metal, n is an integer with a value between 2 and 6, ML.sub.x is an organometallic complex. [0016] The present invention also provides a process for the preparation of an immobilized metal complex catalyst of Formula I wherein M is a Group VIII metal, n is an integer with a value between 2 and 6, ML.sub.x is an organometallic complex, the process comprising pretreating a solid matrix with exterior surface and interior surface, by blocking the exterior surface using a blocking agent in a solvent system leaving the interior surface unperturbed, functionalizing the interior surface of the solid matrix with a functionalized silane, followed by treating the functionalized matrix to treatment with a transition metal complex solution of Formula II wherein M is a Group VIII metal; R1, R2, and R3 are substituents on the phosphine ligand and are selected from hydrogen, alkyl, aryl, arylalkyl, and arylalkyl cycloaromatic group; X is selected from the group consisting of aryl sulphonato, alkyl sulphonato, aryl carbonate, alkyl carbonate, formato, and a halide selected from the group consisting of Cl, Br, I; N--O is a semilabile anionic chelating ligand containing an N donor and an O-- group; 1<n<10; to actually anchor the complex to the interior of the solid matrix, to obtain the immobilized metal complex catalyst. [0017] In an embodiment of the invention the solid matrices comprises a microporous or meosporous material selected from Zeolite Y, Zeolite B, ZSM-5 etc. (microporous), and MCM-41, MCM-48 (mesoporous) respectively. [0018] In another embodiment of the invention, the solid matrix is purely siliceous or is aluminated (containing aluminium in the matrix framework). In another embodiment of the invention the blocking agent used for the blocking of the exterior surface is selected from the gr5roup consisting of an dialkyl and an diaryl substituted dihalosilane having the general formula of R.sub.2SiXI.sub.2, where R is any alkyl, aryl, arylalkyl group etc., and X is a halogen atom selected from CI, Br, and I. In a further embodiment of the invention the solvent system used for the treatment of the matrix to block the exterior surfaces and subsequent functionalization is selected from the group consisting of dichloromethane, diethylether, dry methanol, dry ethanol, cyclohexane, cyclopentane, hexane, pentane and octane. [0019] In yet another embodiment of the present invention, the functionalizing agent used for anchoring the transition metal complex to the pretreated matrices is a functionalized--alkyl-substituted (Z-[CH.sub.2].sub.n--) silane containing at least one alkoxy group (--OR) attached to the silicon atom, having a general formula of Z-(CH.sub.2).sub.n--Si(OR).sub.mH.sub.3-m wherein Z is a functional group selected from the group consisting of --NH.sub.2, --SH, vinyl and allyl, "n" is an integer between 2 and 6, m is an integer between 1 and 3. Continue reading... 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