Heterogeneous catalysts

Abstract

Embodiments of the present disclosure are directed towards a heterogenous catalyst composition formed from using a crystalline porous metal-organic framework (MOF) that reacts in an inverse electron-demand Diels-Alder reaction with a phosphorous ligand to produce a heterogeneous catalyst precursor. The heterogeneous catalyst precursor can react with a Group VIII transition metal catalyst precursor compound to form the heterogeneous catalyst composition that can be used for the hydroformylation of olefins, among other reactions.

Description

HETEROGENEOUS CATALYSTSField of Disclosure

[0001] Embodiments of the present disclosure are directed towards catalysts and in particular heterogeneous catalysts.Background

[0002] Hydroformylation is a process in which olefins are converted to aldehydes in the presence of synthesis gas (carbon monoxide and hydrogen) and a catalyst under appropriate reaction conditions. The resulting aldehydes can then be further converted to any number of compounds, including alcohols, amines, carboxylic acids among other products. Hydroformylation can also be used in the synthesis of fine chemicals for use in pharmaceuticals, cosmetics and electronics, among other areas.

[0003] The catalysts used for hydroformylation have typically been homogeneous catalysts because of their ability to operate at relatively mild temperatures while exhibiting high activity and selectivity. However, many homogenous reactions are not commercially viable because of short catalyst lifetimes and / or recovery problems. For example, depending upon the size or functionality of the olefin involved, different types of hydroformylation purification processes can be used, such as vaporization or distillation processes. When smaller olefins are used, such as propene and 1- butene, a vaporization process affords a straightforward separation of the organic products from the catalyst. However, higher or functional olefins, such as vinyl silanes, cannot be effectively separated with such a technique due to their increased boiling point. In these cases, a distillation process might be used, but the distillation process often results in catalyst decomposition.

[0004] Attention, therefore, has been directed towards the attachment of homogeneous catalysts to solid supports in an attempt to combine the advantages of a heterogenous catalyst separation from the reaction products with the catalytic efficiency of a homogeneous system. Immobilization of the catalyst on a solid support, however, often results in a significant decrease in the selectivity and activity of the catalyst. So, despite the process advantages of heterogeneous catalysts, many reactions are still catalyzed using homogeneous catalysts. As a result, there is a need in the art tofind ways of improving not only the selectivity and the activity of heterogeneous catalysts, but also allowing for heterogeneous catalysts to be separated and recycled.Summary

[0005] The present disclosure addresses the above identified shortcomings by providing heterogeneous catalyst compositions that can provide the selectivity and activity comparable to that of their homogeneous counterpart while also being readily separated from the reaction mixture, providing the possibility for improved catalyst recyclability and lifetime.

[0006] The heterogenous catalyst composition of the present disclosure is formed using a crystalline porous metal-organic framework (MOF) which reacts in an inverse-electron-demand Diels-Alder (IEDDA) reaction with a suitable dienophile bearing a phosphorous ligand to produce a heterogeneous catalyst precursor. The heterogeneous catalyst precursor then reacts with a Group VIII transition metal catalyst precursor compound to form the heterogeneous catalyst composition that can be used for the hydroformylation of olefins, among other reactions. For example, an aldehyde can be produced in the hydroformylation of an olefin in the presence of synthesis gas and the heterogeneous catalyst composition of the present disclosure. Alternatively, the MOF reacts in an IEDDA reaction with a pre-formed metal phosphine complex to directly produce the heterogeneous catalyst composition.

[0007] For the various embodiments, the crystalline porous MOF includes a plurality of non-catalytic metal ions and a plurality of linkers, a plurality of C12 to C20 alkyl moieties, where the plurality of non-catalytic metal ions and the plurality of C 12 to C20 alkyl moieties coordinate with the plurality of linkers to form the crystalline porous MOF. The plurality of linkers are formed from a compound of Formula I:Formula Iwhere each of R and R’ is independently selected from:

[0008] Each of R1and R2are independently selected from -H, C1to C3alkyl, -F, -Cl, -Br,-I, or -CF3; each of R3and R4 are independently selected from -H or C | to C3alkyl, where R3andR4 can form a bridge structure when both are alkyl groups; X is selected from O and S; L ] and L2 are each selected from the group:Each of R5, R6and R7are independently selected from -H -OR10, -COOR1 1-NR12-F, -Cl, -Br, -I, or -CF3, where R10, R1 1and R12are each independently selected from -H or C1to C3alkyl;each R8and R9are independently selected from -H, -OH, -COOH, or -NH2; and A| and A2 are either C or N. For the various embodiments, the plurality of C12 to C20 alkyl moieties can be selected from the group consisting of a C14 alkyl moiety, a C16 alkyl moiety, a C18 alkyl moiety and combinations thereof. In a specific embodiment, the plurality of C 12 to C20 alkyl moieties is a C18 alkyl moiety.

[0009] In one embodiment, each of R and R’ of the crystalline porous MOF is:r the various embodiments,R| is -H, -F or -CF3 and R2 is -H. In an additional embodiment, L| is, where R | is -F or -CF3 and R2 is -H. In another embodiment, I4 is -COOH,R1 is -F and R2 is -H.

[0010] In another embodiment, each of R and R’ is:

[0011] In another embodiment, each of R and R’ is:the various embodiments,R I can be H.

[0012] The plurality of non-catalytic metal ions for the crystalline porous MOF can be selected from the group consisting of nickel (Ni), magnesium (Mg), copper (Cu), cobalt (Co), zirconium (Zr), iron (Fe), zinc (Zn), vanadium (V), aluminum (Al) and combinations thereof. The non-catalytic metal ions are derived from metal ion salts, as discussed herein.

[0013] The heterogenous catalyst precursor is formed from an IEDDA reaction product of the crystalline porous MOF and a dienophile that contains a phosphorous ligand. In one embodiment, the phosphorous ligand can be of Formula II:

[0014] In an alternative embodiment, the phosphorous ligand can be of Formula IV: rmula IV, where the reaction forms the heterogeneous catalyst precursor Formula V, ormula A.

[0015] In an additional embodiment, the phosphorous ligand can be of Formula VI:Formula VI, where the reaction forms the heterogeneous catalyst precursor of Formula VII:

[0016] In an additional embodiment, the phosphorous ligand can be of Formula VIII orFormula C:Formula C and an amine catalyst, where the reaction forms the heterogeneous catalyst precursor of Formula IX:Formula IX.

[0017] With respect to the use of Formula C, an enamine can be generated in situ by condensation of the ketone of Formula C and an appropriate amine catalyst, such as pyrrolidine according to the following reaction:where the IEDDA reaction produces the catalyst precursor of the present disclosure, but eliminates the amine to produce the structure of Formula IX as follows:

[0018] In an additional embodiment, the phosphorous ligand can be of Formula D:Formula D.

[0019] For the above formula II through IX, R16and R17are each independently selected from -H and C1to C3alkyl, and R13- R15are each independently selected from -H, C ] to C3Q alkyl and at least one of:, where n, m, and q are either 0 or 1 and where (n,m,q) is either (1,0,0), (1,1,0), (0,0,1), (0,1,1) or (1,1,1). Each ofthrough R21are selected from C5-C10aryl, C4-C4alkyl or -N(R22)2’ where R22 isselected from -H or C1to C3alkyl. Each of R23 is selected from C5-C10aryl, (4-C4 alkyl, -OR22 or -N(R22)2’ where R22 is selected from -H or C1to C3alkyl. For the variousembodiments, the heterogeneous catalyst precursor can be Formula III and R13 and R|4 can each be diphenylphosphine. For the various embodiments, R13 can be H and R14 can be PPh2-

[0020] The heterogeneous catalyst precursor can then react with a Group VIII transition metal catalyst precursor compound to form the heterogeneous catalyst composition that can be used for the hydroformylation of olefins. For the various embodiments, the Group VIII transition metal catalyst precursor compound is of Formula X:where the M is selected from the group consisting of rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), and osmium (Os). For the various embodiments, L1, L2and L3are each independently selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbomene, chlorine, oxygen, boron, fluoride, bromide, iodide, nitrate, acetate, octanoate, 2-ethylhexanoate, triphenylphosphine (TPP), and acetylacetonate (Ac Ac). For Formula X, w is an integer from 1 to 6, and x, y and z are each independently an integer from 0 to 5 wherein the sum of x, y, and z is at least 1.0. For the various embodiments, the transition metal catalyst of Formula X is selected from the group consisting of RhtO’CsFhMCOh,, bis(norbomadiene)rhodium(I) tetrafluoroborate and bis(l,5-cyclooctadiene)rhodium(I) tetrafluoroborate. Precursors can also include tris(triphenylphosphine)rhodium carbonyl hydride and acety lacetonatoc arbony Itripheny Ipho sphinerhodium(I) .

[0021] For the various embodiments, the present disclosure further provides for a method of forming the heterogeneous catalyst composition that includes reacting the compound of Formula I with a metal acetate to form the crystalline porous MOF; reacting a phosphorous ligand of any one of Formula II, Formula IV, Formula VI or Formula VIII with the crystalline porous MOF in an inverse electron-demand Diels-Alder reaction to form the heterogeneous catalyst precursor of Formula III, Formula V, Formula VII or Formula IX, respectively; and reacting the Group VIII transition metal catalyst precursor compound with the heterogeneous catalyst precursor to form the heterogeneous catalyst composition of the present disclosure.

[0022] For the various embodiments, producing an aldehyde according to the present disclosure is accomplished with a method that includes providing a reaction mixture of an C3to Cl 2 olefin, synthesis gas and the heterogeneous catalyst composition provided herein; and reacting the C3toCl 2 olefin with synthesis gas in the presence of the heterogeneous catalyst composition in a hydroformylation process to produce the aldehyde. For the various embodiments, the hydroformylation process is conducted in a fixed bed process. For the various embodiments, the present disclosure further includes separating the heterogeneous catalyst composition from the reaction mixture after producing the aldehyde using one of a filtration process, a membrane separation process or a centrifuge separation process.

[0023] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list.Brief Description of Drawings

[0024] FIGS. 1A-1D provides crystallinity and porosity of hydrophobic AlTz-68-Cx and AlTz- 68-C18 MOFs.

[0025] FIG. 2 provides a powder x-ray diffractogram (left) and N2 adsorption isotherm (right) of an example catalyst, Rh(NP)(NB)@AlTz-68-C18.

[0026] FIG. 3 provides a31P-CPMAS NMR spectra of NP(NB)@AlTz-68-C18 and Rh(NP)(NB)@AlTz-68-C18 after Rh incorporation.

[0027] FIG. 4 illustrates aldehyde and alkene isomers yield in the hydroformylation of 1 -octene using fixed bed Rh(NP)(NB)@AlTz-68-C18 catalyst, where the line denotes when syngas and 1- octene flow was stopped and then resumed.Detailed Description

[0028] All references to the Periodic Table of the Elements and the various groups therein are to the version published in the CRC Handbook of Chemistry and Physics, 72ndEd. (1991-1992) CRC Press, at page 1-11.

[0029] Unless stated to the contrary, or implicit from the context, all parts and percentages are based on weight and all test methods are current as of the filing date of this application. Forpurposes of United States patent practice, the contents of any referenced patent, patent application or publication arc incorporated by reference in their entirety (or its equivalent US version is so incorporated by reference) especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0030] As used herein, “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably. The terms “comprises,” “includes,” and variations thereof do not have a limiting meaning where these terms appear in the description and claims. Thus, for example, an aqueous composition that includes particles of “a” hydrophobic polymer can be interpreted to mean that the composition includes particles of “one or more” hydrophobic polymers.

[0031] As used herein, the term “ppm” means pails per million by weight.

[0032] As used herein, “Ph” is phenyl or substituted phenyl.

[0033] As used herein, the term “aryl” as used herein is a group containing any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, anthracene, and the like. The aryl group may be substituted or unsubstituted. Aryl groups are alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, — NH2, carboxylic acid, ester, ether, as described herein. It may be substituted with one or more groups including but not limited to halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo or thiol. The term “biaryl” is a specific type of aryl group and is included in the definition of “aryl”. Furthermore, an aryl group can be a single ring structure, or a plurality of rings that are either fused ring structures or linked via one or more bridging groups, such as carbon-carbon bonds. Includes structure. For example, a biaryl is bonded together via a fused ring structure, as in naphthalene, or via two or more carboncarbon bonds, as in biphenyl. Refers to an aryl group.

[0034] As used herein, the term “alkyl” is a branched (when possible) or unbranched saturated hydrocarbon group of the number of carbon atoms specified. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be substituted or unsubstituted.

[0035] For purposes of this disclosure, the term “hydrocarbon” is contemplated to include all permissible compounds having at least one hydrogen and one carbon atom. Such permissiblecompounds may also have one or more heteroatoms. In a broad aspect, the permissible hydrocarbons include acyclic (with or without hctcroatoms) and cyclic, branched and unbranchcd, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds which can be substituted or unsubstituted.

[0036] As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds unless otherwise indicated. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which the number of carbons can range from 1 to about 20 or more, alternatively from 1 to about 12. The permissible substituents can be one or more and the same or different for appropriate organic compounds.

[0037] Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed in that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). For the purposes of the present disclosure, it is to be understood, consistent with what one of ordinary skill in the ail would understand, that a numerical range is intended to include and support all possible subranges that are included in that range. For example, the range from 1 to 100 is intended to convey from 1.01 to 100, from 1 to 99.99, from 1.01 to 99.99, from 40 to 60, from 1 to 55, etc.

[0038] As used herein, the term “hydroformylation” is contemplated to include, but not limited to, all permissible asymmetric and non-asymmetric hydroformylation processes that involve converting one or more substituted or unsubstituted olefinic compounds or a reaction mixture comprising one or more substituted or unsubstituted olefinic compounds to one or more substituted or unsubstituted aldehydes or a reaction mixture comprising one or more substituted or unsubstituted aldehydes.

[0039] Embodiments of the present disclosure provide for a heterogenous catalyst composition formed from a phosphorus ligand, covalently bound to a crystalline porous metal-organic framework (MOF), where the phosphorus ligand binds a transition metal catalyst precursor compound to provide the heterogenous catalyst composition of the present disclosure. As discussed herein, the phosphorous ligand of the present disclosure provides for design control (e.g., control of steric and electronic properties) that can lead to desirable selectivity and activity from theheterogeneous catalyst composition of the present disclosure. The crystalline porous MOF of the present disclosure is composed of inorganic clusters (e.g., non-catalytic metal ions) connected by linkers bearing a tetrazine group, as discussed herein. The crystalline porous MOF are also formed with a plurality of C12 to C20 alkyl moieties, where the plurality of non-catalytic metal ions and the plurality of C12 to C20 alkyl moieties coordinate with the linkers to form the crystalline porous MOF. The crystalline porous MOF provides a solid-state crystalline and porous network on which to modulate and tune the design control of the phosphorous ligand. The crystalline porous MOF also provides the solid phase that allows for the heterogenous catalyst composition of the present disclosure to be readily separated from the reaction mixture (e.g., olefins, aldehydes and synthesis gas in a hydroformylation reaction), thus improving catalyst recyclability and lifetime.

[0040] For the various embodiments, the present disclosure utilizes what is referred to herein as a tetrazine based “click-grafting” reaction to covalently link the phosphorus ligand of the present disclosure to the crystalline porous MOF to form what is referred to herein as the heterogenous catalyst precursor. Until this disclosure, one issue with trying to covalently bond a phosphorous ligand to a conventional MOF is that phosphorus ligands are generally prone to decompose in the harsh synthesis conditions used in forming the MOFs (often by oxidation or hydrolysis). The phosphorus ligands can also compete with the linker for coordination to the non-catalytic metal clusters in the MOF, which is not desirable.

[0041] To address the above noted issues, the present disclosure uses the tetrazine based “clickgrafting” reaction to covalently bond the phosphorus ligand to a tetrazine moiety that is present on the crystalline porous MOF of the present disclosure. The advantage of the tetrazine-based clickgrafting reaction are that it is rapid, traceless, and forms strong covalent bonds, which allow the phosphorus ligand to be firmly anchored to the crystalline porous MOF without disrupting its porous crystalline structure. Another advantage of the click grafting procedure is that the phosphorous moieties do not interfere or react with the components of the click grafting process

[0042] The tetrazine-based click-grafting reaction of the present disclosure proceeds via a 4+2 cycloaddition reaction (e.g., an IEDDA reaction) that rapidly and selectively bonds the phosphorous ligand to the tetrazine moiety in the crystalline porous MOF. To facilitate this reaction, the phosphorous ligand of the present disclosure includes what is referred to herein as a “click-reaction partner,” which can be a strained and / or electron rich dienophile (i.e., a compound having amultiple bond such as an alkene, an alkyne, an allyl, an enamines, or enol ether) that reacts with the tctrazinc moiety in the crystalline porous MOF. Such a reaction occurs under mild conditions, where only a nitrogen (N2) byproduct is produced in forming the heterogenous catalyst precursor of the present disclosure. The phosphorus ligand of the present disclosure further includes a reaction moiety that reacts with a Group VIII transition metal catalyst precursor compound, as provided herein, to form the heterogenous catalyst of the present disclosure.

[0043] As provided herein, the heterogenous catalyst of the present disclosure can have the activity and selectivity of their homogeneous counterpart. The heterogeneous catalyst composition of the present disclosure may be useful in a broad classes of reactions such as hydroformylation, carbonylation of alcohols, cross-coupling and asymmetric hydrogenation, and olefin (e.g., ethylene) oligomerization, among other reactions provided herein.

[0044] The present disclosure provides for heterogeneous catalyst compositions that can provide the selectivity and activity comparable to that of their homogeneous counterpail while also being readily separated from the reaction mixture, providing the possibility for improved catalyst recyclability and lifetime. The heterogenous catalyst of the present disclosure is formed from using the crystalline porous MOF that reacts in an IEDDA reaction with a suitable dienophile containing the phosphorous ligand to produce the heterogeneous catalyst precursor. The heterogeneous catalyst precursor then reacts with the Group VIII transition metal catalyst precursor compound to form the heterogeneous catalyst composition that can be used for the hydroformylation of olefins. Alternatively, the MOF reacts in an IEDDA reaction with a pre-formed metal phosphine complex to directly produce the heterogeneous catalyst composition. The above components of the present disclosure are disclosed as follows.Crystalline Porous MOF

[0045] The crystalline porous metal-organic framework (MOF) of the present disclosure can be a one-dimensional porous structure, a two-dimensional porous structure, or a three-dimensional porous structure composed of three major components: (a) linkers (sometimes referred to as “struts” or “ligands”) that coordinate to (b) a plurality of non-catalytic metal ions (sometimes referred to as “clusters” or “nodes” or “secondary building units (SBUs)”) and (c) a plurality of C12 to C20 alkyl moieties, where the plurality of non-catalytic metal ions and the plurality of Cl 2 to C20 alkylmoieties coordinate with the plurality of linkers to form the crystalline porous MOF. For the various embodiments, the crystalline porous MOF includes the plurality of non-catalytic metal ions, the plurality of linkers and the plurality of C 12 to C20 alkyl moieties, where the plurality of non- catalytic metal ions and the plurality of C 12 to C20 alkyl moieties coordinate with the plurality of linkers to form the crystalline porous MOF. The crystalline porous MOFs possess highly ordered structures with significantly high surface areas. Alternatively, the crystalline porous MOF of the present disclosure is highly porous. The crystalline porous MOF of the present disclosure can take the form of various particles (e.g., flakes, rods, needles, etc.). As discussed herein the plurality of C12 to C20 alkyl moieties helps to impart a hydrophobic property to the crystalline porous MOF, which surprisingly has led to heterogeneous catalyst compositions having improved performance in the areas of both increased hydroformylation efficiencies (e.g., increased efficiencies for the hydroformylation of 1 -octene to 1 -nonanal as seen in the Examples section below) and the reduction of olefin isomerization during the hydroformylation reaction.

[0046] The crystalline porous MOF described herein comprise the plurality of non-catalytic metal ions forming the nodes or clusters, which may be formed with at least one metal selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn, Al, In, Ga, Sn, Bi, Pb, Tl, Zn, Cd, Hg Be, Mg, Ca, Sr, Ba, and Ra. Alternatively, the plurality of non-catalytic metal ions for the crystalline porous MOF can be selected from the group consisting of nickel (Ni), magnesium (Mg), copper (Cu), cobalt (Co), zirconium (Zr), iron (Fe), zinc (Zn), vanadium (V), aluminum (Al) and combinations thereof. In an alternative embodiment, the non-catalytic metal is Ni, Mg and / or Zr. For the various embodiments, the non-catalytic metal ion may have any number of its possible oxidation states (e.g., M+' , M+^, M+3). The non-catalytic metals provided herein are not relied upon to be catalytically active as they do not have a directly bonded phosphorous ligand.

[0047] For the various embodiments, the choice of the non-catalytic metal ion, the plurality of C 12 to C20 alkyl moieties and the linker arm help dictate the structure and properties of the crystalline porous MOF. For example, the non-catalytic metal ion’s coordination preference influences the size and shape of the pores of the crystalline porous MOF by dictating how many linkers can bind to the non-catalytic metal cluster or nodes and in which orientation. For the various embodiments, the linkers of the present disclosure can be multidentate, having at least twodonor atoms (i.e., bidentate atoms such as -N, -O, and / or -S) and being neutral or anionic. The structure of the crystalline porous MOF can also be affected by the shape, length, and functional groups present in the linker arm.

[0048] For the various embodiments, the plurality of linkers are formed from a compound of Formula I:Formula I where each of R and R’ is independently selected from:

[0049] Preferably, R and R’ are the same moiety. Alternatively, R and R’ can be different moictics. For the various embodiments, the selection of the moiety for R and R’ can be based on a desired length and geometry of the linker, where the length and geometry of the linker can allow for the design and tailoring of the porosity and dimensional structure of the resulting crystalline porous MOF.

[0050] For the various embodiments, each of R1and R2are independently selected from -H, C1to C3alkyl, -F, -Cl, -Br, -I, or -CF3; each of R3and R4 are independently selected from -H or Ci to C3alkyl, where R3and R4 can form a bridge structure when both are alkyl groups; X is selected from O and S; Li and L2 are each selected from the group:Each of R5, R8and R7 are independently selected from -H -OR10, -COORn, -NR12 -F, -Cl, -Br, -I, or — CF3, where R10, R1 1and R12 are each independently selected from -H or C | to C3alkyl; each R8and R9arc independently selected from -H, -OH, -COOH, or -NH2; and A| and A2 arc either C or N.

[0051] In one embodiment, each of R and R’ of the crystalline porous MOF is:r the various embodiments,R| is -H, -F or -CF3 and R2 is -H. In an additional embodiment, L1is, where R | is -F or -CF3 and R2 is -H. In another embodiment, L j is -COOH,R I is -F and R2 is -H.

[0052] In another embodiment, each of R and R’ is:

[0053] In another embodiment, each of R and R’ is:the various embodiments, R | can beH.

[0054] Preparation of linkers are readily available to one of ordinary skill in the art.Examples of producing the linkers are provided in the Examples section herein. Typically, the linkers formed from a compound of Formula I are produced by oxidation of a dihydrotetrazine precursor. Examples of oxidizing agents for conversion of the dihydrotetrazine precursor to the tetrazine linker include isoamyl nitrite, hydrogen peroxide,dichloro-5,6-dicyano-l,4-benzoquinone (DDQ), N-bromo succinimide (NBS), oxygen, among others. Typically, the dihydrotetrazine precursor is produced by Pinner synthesis involving thecondensation of two equivalents of an aryl nitrile with hydrazine hydrate. The Pinner synthesis can be catalyzed by a sulfur catalyst or a Lewis acid. Examples of sulfur catalysts include Ss andN- acetylcysteine. Examples of Lewis acid catalysts include metal salts of nickel and zinc. Alternatively, the dihydrotetrazine precursor to the linkers formed from a compound of Formula I are produced by reaction of imidoesters with hydrazine, or by treatment of acylhydrazides with PCI5 and subsequent condensation with tetrazine, or by cyclization of a thiocarbohydrazide with a carboxylic acid or trithiocarbonate. With respect to their geometric shape, the crystalline porous MOF may be in the form of polyhedral crystals, cubic, hexagonal or octahedral in shape. For the various embodiments, each linker of the crystalline porous MOF can connect to two or more of the nodes of the plurality of non-catalytic metal ions. Such a configuration allows for each node of the plurality of non-catalytic metal ions to be coordinated in an octahedral geometry with, for example, twelve linkers. Alternatively, the configuration can allow for each node of the plurality of non- catalytic metal ions to be coordinated in a cubic or hexagonal geometry.

[0055] For the various embodiments, the crystalline porous MOF of the present disclosure can have a Brunauer-Emmet-Teller (BET) surface area of 500 to 5000 rn^ / g. Alternatively, the crystalline porous MOF of the present disclosure can have a BET surface area of 1000 to 4000 rn2 / g. BET surface area is measured according to S. Brunauer, P. H. Emmett, E. Teller, J. Am. Chem. Soc. 1938, 60, 309-319, incorporated herein by reference, using nitrogen gas adsorption analysis. Pore diameters for the crystalline porous MOF of the present disclosure can range from 0.1 nanometers (nm) to 5 nm, where there can be a mixture of pore diameters. Pore diameters can also range from 0.9 nm to 3 nm. For some embodiments, pore size distribution (PSD) is determined from nitrogen gas adsorption data using the Barrett, Joyner, and Halenda (BJH) method according to E. P. Barrett, L. G. Joyner, P. P Halenda, J. Am. Chem. Soc. 1951, 73, 1, 373-380, incorporated herein by reference. Alternatively, PSD is determined from nitrogen gas adsorption data using nonlinear’ density functional theory (NLDFT) models according to N.A. Seaton, J.P.R.B. Walton, N. Quirke, Carbon, 1989, 27, 6, 853-861, incorporated herein by reference.

[0056] For the various embodiments, a single type of linker arm is used in forming the crystalline porous MOF of the present disclosure to provide the crystalline porous MOF with an undistorted geometry. In alterative embodiment, a first type of linker arm and a second type of linker arm (e.g., the second type of linker arm is longer than the first linker arm) are used so that thecrystalline porous MOF has a distorted geometry. Additional types of linkers might also be used, as desired, to provide additional distorted geometries for the crystalline porous MOF.

[0057] The crystalline porous MOF can be formed according to a number of different processes. Examples of such processes include, but are not limited to solvothermal methods, mechanochemical methods, electrochemistry methods, assisted synthesis methods (z’.e., by ultrasound or microwave), and subcritical water methods. For example, the crystalline porous MOF can be produced by a solvothermal method. Typically, a solvothermal synthesis comprises the reaction of one or more metal salts and one or more linkers, as provided herein, in the presence of organic solvents or mixtures, alternatively involving formamides, alcohols, or pyrrolidones.Parameters in the solvothermal synthesis include, but are not limited to, temperature, concentration of reactants (which can be varied over a wide range) and pH of the reaction solution. The method can include mixing a source of the plurality of non-catalytic metal ions, the linkers, an organic solvent, and water to produce a reaction mixture. The reaction mixture can be allowed to react for the time and temperature provided herein, where the reaction can occur under an atmosphere of room air and at atmospheric pressure. It is possible, however, that depending on the non-catalytic metal ion and linker arm, synthesis of the crystalline porous MOF may require use of an inert atmosphere like nitrogen gas (N2).

[0058] Examples of the metal ion salts of the metals provided herein include, but are not limited to, nitrates, chlorates, sulfates, phosphates, molybdates, chromates, arsenites, acetates, bromides, chlorides, fluorides, silicates, iodides, methacrylates, among other, including their hydrated salt. Specific examples of such metal ion salts includes, but are not limited to, Ni(OAc)2,Ni(NO3)2, ZrCl4, ZrOCl2, ZnCl2, Mg(NO3)2, FeCl2and FeCl3.

[0059] For the various embodiments, when forming the crystalline porous MOF the reaction mixture can contain a molar excess of the non-catalytic metal ion as compared to the linker arm. In one embodiment, a molar ratio of the non-catalytic metal ion to the linker arm in the mixture can be in a range of 1 : 1 to 2 : 1 , alternatively 1.1 : 1 to 1.5 : 1 , or about 1.2 : 1 to 1.3 : 1. In one embodiment, non-catalytic metal ion is present in the reaction mixture at a concentration in a range of 0.05 to 0.5 M, alternatively 0.08 to 0.3 M, alternatively about 0.1 M.

[0060] In one embodiment, the organic solvent may be one or more solvents selected from ethers (e.g. diethyl ether, tetrahydrofuran, 1,4-dioxane, tetrahydropyran, t-butyl methyl ether,cyclopentyl methyl ether, di-iso-propyl ether), glycol ethers (e.g., 1 ,2-dimethoxyethane, diglyme, triglymc), alcohols (e.g., methanol, ethanol, trifluorocthanol, n-propanol, i-propanol, n-butanol, i- butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl-2-butanol, 2-trifluoromethyl-2-propanol, 2,3- dimethyl-2-butanol, 3-pentanol, 3-methyl-3-pentanol, 2-methyl-3-pentanol, 2-methyl-2-pentanol, 2,3-dimethyl-3-pentanol, 3-ethyl-3-pentanol, 2-methyl-2-hexanol, 3-hexanol, cyclopropylmethanol, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol), aromatic solvents (e.g., benzene, o- xylene, m-xylene, p-xylene, mixtures of xylenes, toluene, mesitylene, anisole, 1,2- dimethoxybenzene, a,a,a-trifluoromethylbenzene, fluorobenzene), chlorinated solvents (e.g., chlorobenzene, dichloromethane, 1,2-dichloroethane, 1,1 -dichloroethane, chloroform), ester solvents (e.g., ethyl acetate, propyl acetate), amide solvents (e.g., dimethylformamide, diethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone), urea solvents, ketones (e.g. acetone, butanone), acetonitrile, propionitrile, butyronitrile, benzonitrile, dimethyl sulfoxide, ethylene carbonate, propylene carbonate, l,3-dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidinone, and mixtures thereof. The solvent may be selected from non-polar solvents (e.g., hexane, benzene, toluene, diethyl ether, chloroform, 1,4-dioxane), polar aprotic solvents (e.g., ethyl acetate, tetrahydrofuran, dichloromethane, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide) and polar protic solvents (e.g., acetic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, formic acid, water) and mixtures thereof. Alternatively, the solvent is dimethylformamide (DMF) and water.

[0061] After the mixing, the reaction mixture is heated to produce a precipitate. The reaction mixture is heated at a temperature in a range of 100 to 180 °C, alternatively 120 to 170 °C, alternatively 130 to 160 °C or alternatively 145 to 155 °C for a time in a range of 1 hour to 5 days, alternatively 1 hour to 3 days (72 hours), alternatively about 24 hours to 48 hours. In one embodiment, the reaction mixture may be heated in a microwave oven or in an autoclave (or other enclosed vessel) at an elevated pressure. In one embodiment, the reaction mixture may be continually mixed or agitated during the heating. Alternatively, the reaction mixture may not be disturbed during the heating.

[0062] For the various embodiments, the use of a modulator in the reaction mixture is also possible. As used herein, a modulator is used to control the crystal growth in the crystalline porous MOF of the present disclosure. For the various embodiments, the modulator is often a monotopicanalog to the linker arm (e.g., benzoic acid for a carboxylate MOF) and is often acidic, such that the modulator either competes with the linker arm for non-catalytic metal ion coordination, or the modulator lowers the pH and thus concentration of deprotonated linker arm. Basic modulators can also be used to promote the crystalline porous MOF formation by deprotonating highly basic linkers. Examples of the modulator includes, but is not limited to, benzoic acid, acetic acid, HO, pyrazole, amines and pyridine.

[0063] The heating produces a precipitate comprising crystals of the crystalline porous MOF. Preferably, after the step of heating the reaction mixture, the reaction mixture is allowed to cool to room temperature. The crystalline porous MOF may be isolated and purified by methods known to those of ordinary skill in the art, such a filtration, decantation, aqueous work-up, extraction with organic solvents, on normal phase or reversed phase. The crystalline porous MOF may be rinsed with an organic solvent such as those previously mentioned, and then hydrophobically modified with the plurality of C 12 to C20 alkyl moieties.

[0064] For the various embodiments, the plurality of C12 to C20 alkyl moieties can help to dictate the hydrophobic nature of the crystalline porous MOF, produced as discussed herein, and the heterogeneous catalyst compositions of the present disclosure formed therefrom. For the various embodiments, the plurality of C12 to C20 alkyl moieties are selected from the group consisting of a C14 alkyl moiety, a C16 alkyl moiety, a Cl 8 alkyl moiety and combinations thereof. In a specific embodiment, the plurality of C 12 to C20 alkyl moieties is a C18 alkyl moiety. For the various embodiments, the plurality of C12 to C20 alkyl moieties (e.g., the C12 alkyl moiety, the C14 alkyl moiety, the C16 alkyl moiety, the C18 alkyl moiety and the C20 alkyl moiety), can be selected from the group consisting of linear alkyls, branched alkyls and combinations thereof. Examples of linear alkyls for the present disclosure include, but are not limited to, 1 -dodecene, 1 -tetradecene, 1- hexadecene, 1 -octadecene and 1-eicosene.

[0065] With respect to hydrophobically modifying the crystalline porous MOF with the plurality of C12 to C20 alkyl moieties, as provided herein, the alkyl moiety, or moieties, can be mixed with an organic solvent (e.g., be suspended in diethyl ether, or other organic solvent(s) as provided above) to form an alkyl reagent. For the various embodiments, the alkyl reagent can be added at a volume ratio of 20 to 300 versus MOF precursor, where the MOF precursor for this volume ratio is in an organic solvent (e.g., diethyl ether) at 50 to 500 ml of solvent per gram ofMOF. The crystalline porous MOF formed from the linkers coordinating to the plurality of non- catalytic metal ions arc mixed with the alkyl reagent to form a suspension in which the alkyl moieties hydrophobically modify the crystalline porous MOF. This hydrophobic modification of the crystalline porous MOF can take place at a temperature in the range of 20 to 60 °C, at a pressure of atm pressure Pa and for a time of 0.5 to 5 hrs. The time and temperature used for the hydrophobic modification of the crystalline porous MOF influences the hydrophobicity of the resulting crystalline porous MOF and the heterogeneous catalyst composition. Upon completing the time for the hydrophobic modification, the resulting crystalline porous MOF can be separated from the alkyl reagent. Separation can be achieved using known techniques as discussed herein, such as centrifugation and / or filtration. The crystalline porous MOF can then be rinsed with fresh organic solvent (e.g., a neat version of the organic solvent used in the alkyl reagent), after which the crystalline porous MOF can be dried. Drying of the crystalline porous MOF can take place at a temperature of 20 to 80 °C for 6 to 24 hrs. The crystalline porous MOF for use in forming the heterogeneous catalyst composition can then be activated. In one embodiment, the crystalline porous MOF is activated at a temperature in a range of 40 to 150 °C under a high vacuum 0.00001 to 1 Pascal (Pa) for 8 to 72 hours.Heterogenous Catalyst Precursor

[0066] The heterogenous catalyst precursor of the present disclosure is formed as the reaction product of the crystalline porous MOF and a phosphorous ligand using an inverse electrondemand Diels-Alder (IEDDA) reaction. The reaction is referred to herein as a tctrazinc based clickgrafting reaction that covalently links the phosphorus ligand, as provided herein, to the crystalline porous MOF to form the heterogenous catalyst precursor of the present disclosure. The IEDDA reaction is a cycloaddition reaction that forms two new chemical bonds from the reaction between an electron-rich dienophile and an electron-poor diene. The IEDDA reaction occurs extremely rapidly (e.g., second order reaction kinetics between 800 M-Is- 1and 30000 M- Is-1). In the present disclosure, the IEDDA reaction proceeds between a strained and / or electron-rich alkene and a tetrazine moiety located on the linker arm of the present disclosure.

[0067] As is known in the art, the IEDDA reaction is very rapid yet proceeds under very mild conditions, producing nitrogen gas (N2) as the sole reaction by-product. Reaction temperaturesfor the IEDDA reaction are, for example, in a range of 20 to 150 °C. Preferably the reaction temperatures are in a range of 40 to 60 °C. for the IEDDA reaction are in a range of 30 to 70 °C. Most preferably the reaction temperatures for the IEDDA reaction

[0068] For the various embodiments, the IEDDA reactions are conducted under an inert atmosphere, where an N2 atmosphere is one example. The IEDDA reactions can also be conducted under atmosphere air. For the various embodiments, the crystalline porous MOF is suspended in an organic solvent, as provided herein, to which the phosphorous ligand of the present disclosure is added. Preferably, the solvent for the tetrazine based click-grafting reaction can be selected from chlorinated solvents such as dichloromethane, chlorobenzene, 1,2-dichloroethane, 1,1- dichloroethane, chloroform, and mixtures thereof. In addition, preferred solvents possess a moderate dipole moment (e.g., polar solvents, such as dimethylformamide among others). Such solvents can also include mixtures of the above noted solvents with one or more of a protic solvent which can include water.

[0069] For the tetrazine based click-grafting reaction, the crystalline porous MOF can be provided in a molar equivalent or molar excess relative the phosphorus ligand. For example, the range of the molar amounts of the tetrazine present in the crystalline porous MOF to the dienophile of the phosphorous ligand can be from 1:1 to 1000:1. Preferably, the range of the molar amounts of the tetrazine present in the crystalline porous MOF to the dienophile of the phosphorous ligand is from 1:1 to 100:1, and more preferably from 1:1 to 13:1, where a value of 10:1 is possible. For the tetrazine based click-grafting reaction, the crystalline porous MOF can be provided in a molar equivalent or molar excess relative the dienophile appended phosphorus ligand. For example, the range of the molar amounts of the tetrazine present in the crystalline porous MOF to the dienophile of the phosphorous ligand can be from 1:1 to 1000:1. Other suitable dienophiles can include an enamine, as are known, where the amount of amine to ketone used in forming the enamine can be from 1000:1 to 1:1, preferably 10:1.

[0070] The IEDDA reaction mixture of the crystalline porous MOF and the phosphorus ligand is allowed to react under the inert atmosphere (e.g., an N2 atmosphere) for a reaction time of 1 day to 5 days at the desired reaction temperature. For example, the IEDDA reaction mixture of the crystalline porous MOF and the phosphorus ligand is heated to the desired reaction temperature (e.g., 25 °C) under an inert atmosphere for 48 hours (2 days). After the reaction time, the resultingheterogenous catalyst precursor is washed with and subsequently allowed to soak in fresh organic solvent, as provided herein (e.g., dichloromethane), at room temperature (23 °C). Soaking times for the heterogenous catalyst precursor can be from 30 minutes to 120 minutes. The heterogenous catalyst precursor is then activated at a temperature in a range of 30 to 100 °C under a high vacuum 0.00001 to 1 KPa for 12 to 24 hours. Preferably, the temperature for activating the heterogenous catalyst precursor can be from 40 to 90 °C.

[0071] In an additional embodiment, tetrazine groups remaining in the heterogenous catalyst precursor can be reacted with norbornene to avoid side reactions or decomposition of any tetrazine groups remaining in the heterogenous catalyst precursor. The treatment is performed by suspending the heterogenous catalyst precursor in an organic solvent, as provided herein (e.g., dichloromethane), with a molar excess of norbornene under an inert atmosphere (e.g., an N2 atmosphere). The mixture is heated to 40 to 70 °C for 8 to 20 hours. After which time, the heterogenous catalyst precursor is washed with fresh organic solvent (e.g., dichloromethane) and then fresh hexanes, where the heterogenous catalyst precursor is allowed to soak in each wash for at least 1 hour. The heterogenous catalyst precursor is then activated as discussed above.

[0072] The following are examples of the click-reaction partner having a strained dienophile, as discussed herein, that can react with the tetrazine moiety in the crystalline porous MOF. Examples provided herein can be didentate or mono-dentate. In one embodiment, the phosphorous ligand can be of Formula II:Formula II, where the IEDDA reaction as discussed herein forms the heterogeneous catalyst precursor of Formula III:

[0073] In an alternative embodiment, the phosphorous ligand can be of Formula IV:.

[0074] In an additional embodiment, the phosphorous ligand can be of Formula VI:Formula VI where the IEDDA reaction forms the heterogeneous catalyst precursor of Formula VII.

[0075] In an additional embodiment, the phosphorous ligand can be of Formula VIII orFormula C:Formula VIII orFormula C and an amine catalyst, where the reaction forms the heterogeneous catalyst precursor of Formula IX:.

[0077] With respect to the use of Formula C, an enamine can be generated in situ by condensation of the ketone of Formula C and an appropriate amine catalyst, such as pyrrolidine, according to the following reaction:where the IEDDA reaction produces the catalyst precursor of the present disclosure, but eliminates the amine to produce the structure of Formula IX as follows:For example, when 3-(diphenylphosphine)cyclopentanone (Formula D) is used, the following reaction according to the present disclosure, is possible:

[0078] For the above formulae A and II through IX, R16and R 17 are each independently -H and C1to C3alkyl, and R 13 - R15are each independently selected from -H, C | to C30alkyl and at least one of:

[0079] Preferably, for the above formulae II through IX, R15is selected from -H, C1to C30alkyl and R 13and R14are each independently selected from:Preferably, R13and R14are each the same moiety.For the various embodiments, each of n, m, and q are either 0 or 1, where for the above moieties the variables (n,m,q) are either (1,0,0), (1,1,0), (0,0,1), (0,1,1) or (1,1,1). For the various embodiments, each of R18 through R21are selected from C5-C10aryl, C1-C4 alkyl or -N(R22)2’ where R22 is selected from -H or C4 to C3alkyl. Each of R23 is selected from C5-C40 aryl, C1- C4 alkyl, -OR22 or -N(R22)2’ where R22 is selected from -H or C | to C3alkyl.Heterogeneous Catalyst Composition

[0080] The heterogeneous catalyst precursor, as provided herein, can then react with a Group VIII transition metal catalyst precursor compound to form the heterogeneous catalyst composition. As discussed herein, the heterogeneous catalyst composition of the present disclosure can be used in any number of reactions, including hydroformylation, carbonylation of alcohols, cross-coupling and asymmetric hydrogenation, and ethylene oligomerization, among others.

[0081] For the various embodiments, the Group VIII transition metal catalyst precursor compound is of Formula X:Formula X where the M is selected from the group consisting of rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), and osmium (Os).

[0082] For the various embodiments, L1, L2and L3are each independently selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, oxygen, boron, fluoride, bromide, iodide, nitrate, acetate, octanoate, 2-ethylhexanoate, triphenylphosphine (TPP), and acetylacetonate (Ac Ac).

[0083] For Formula X, w is an integer from 1 to 6, and x, y and z are each independently an integer from 0 to 5 wherein the sum of x, y, and z is at least 1.0.

[0084] For the various embodiments, the transition metal catalyst precursor of Formula X iscombinations thereof.

[0085] For the reaction between the heterogeneous catalyst precursor and the Group VIII transition metal catalyst precursor compound to form the heterogeneous catalyst composition, the heterogeneous catalyst precursor and the Group VIII transition metal catalyst precursor compound are mixed with a solvent. The solvent can be selected from the group consisting of toluene, acetonitrile and dimethylformamide among others. Such solvents can also include mixtures of the above noted solvents.

[0086] The reaction is preferably conducted under the inert atmosphere (e.g.. an N2 atmosphere) for a reaction time of 1 hour to 5 days at the given reaction temperature. Preferably, the reaction time is from 24 hours to 48 hours. The reaction can take place at a temperature, for example, in a range of 20 to 150 °C. Preferably the reaction temperatures is in a range of 20 to 70 °C. Most preferably the reaction temperature is in a range of 25 to 50 °C.

[0087] Preferably, for the reaction the heterogeneous catalyst precursor is provided in a molar excess (based on phosphorous content) relative the Group VIII transition metal catalyst precursor compound, where phosphorous content can be measured by known analytical methods or could be on a mass balance basis. For example, the heterogeneous catalyst precursor is provided in a molar excess of 1:0.001 to 1:0.25 relative to the Group VIII transition metal catalyst precursor compound. Preferably, the heterogeneous catalyst precursor is provided in a molar excess of 1:0.01 to 1:0.25 relative to the Group VIII transition metal catalyst precursor compound. More preferably, the heterogeneous catalyst precursor is provided in a molar excess of 1:0.1 to 1:0.25 relative to the Group VIII transition metal catalyst precursor compound. Most preferably, the heterogeneous catalyst precursor is provided in a molar excess of 1:0.1 to 1:0.2 relative to the Group VIII transition metal catalyst precursor compound. Such a molar excess of the Group VIII transition metal catalyst precursor compound relative to the heterogeneous catalyst precursor better ensures that the Group VIII transition metal catalyst precursor compound is bound to the sites of the heterogeneous catalyst precursor, where any free Group VIII transition metal catalyst precursor compounds are more likely to bind or be re-bound to the heterogeneous catalyst precursor.

[0088] After the reaction time, the resulting heterogenous catalyst precursor is washed with and subsequently allowed to soak in fresh organic solvent at room temperature (23 °C). Soaking times for the heterogenous catalyst precursor can be from 30 minutes to 120 minutes. The heterogenous catalyst precursor is then activated at a temperature in a range of 30 to 100 °C under a high vacuum 0.00001 to 1 Pa for 12 to 24 hours. Preferably, the temperature for activating the heterogenous catalyst precursor can be from 40 to 90 °C.Reactions and Reactors

[0089] As provided herein, the heterogeneous catalyst composition of the present disclosure may be useful in a broad classes of reactions such as hydroformylation, carbonylation of alcohols, cross-coupling and asymmetric hydrogenation, and olefin oligomerization, among other reaction provided here. Other illustrative reactions include, for example, hydroacylation (intramolecular and intermolecular), hydrocyanation, hydroamidation, hydroesterification, aminolysis, alcoholysis, hydrocarbonylation, olefin isomerization, transfer hydrogenation and the like. Preferred processes involve the reaction of organic compounds with carbon monoxide, or with carbon monoxide and athird reactant, e.g., hydrogen, or with hydrogen cyanide, in the presence of a catalytic amount of the heterogeneous catalyst composition of the present disclosure. The most preferred processes include hydroformylation, hydrocyanation, hydrocarbonylation, hydroxycarbonylation and carborlylation.

[0090] The permissible starting material reactants encompassed by the processes provided herein are, of course, chosen depending on the particular’ process desired. Such starting materials are well known in the art and can be used in conventional amounts in accordance with conventional methods. Illustrative starting material reactants include, for example, substituted and unsubstituted aldehydes, (intramolecular’ hydroacylation), olefins (hydroformylation, carbonylaltion, intermolecular hydroacylation, hydrocyanation, hydroamidation, hydroesterification, aminolysis, alcoholysis), ketones (transfer hydrogenation), epoxides (hydroformylation, hydrocyanation), alcohols (carbonylation) and the like. Illustrative of suitable reactants for effecting the processes of this disclosure are set out in Kirk-Othmer, Encyclopedia of Chemical Technology, Fifth Edition, 2004, the pertinent portions of which are incorporated herein by reference.

[0091] A preferred process useful with the heterogeneous catalyst composition of the present disclosure is hydroformylation. The hydroformylation processing techniques may correspond to known processing techniques. The hydroformylation products may be asymmetric, non-asymmetric or a combination thereof, with the preferred products being non-asymmetric. The process may be conducted in a batch, a continuous or semi-continuous fashion and in some embodiments, involve a catalyst liquid recycle operation. Processes can also include those involving catalyst liquid recycle hydroformylation processes. In general, such catalyst liquid recycle hydroformylation processes involve the production of aldehydes by reacting an olefinic unsaturated compound with carbon monoxide and hydrogen in the presence of the heterogeneous catalyst composition of the present disclosure in a liquid medium that also contains a solvent for the catalyst and ligand. Preferably free heterogeneous catalyst precursor can be present in the liquid hydroformylation reaction medium. The recycle procedure generally involves withdrawing a portion of the liquid reaction medium containing the heterogeneous catalyst composition and aldehyde product from the hydroformylation reactor (i.e., reaction zone), either continuously or intermittently, and recovering the aldehyde product therefrom in accordance with known separation techniques. Such techniques can include, but are not limited to, sedimentation, filtration, membraneand / or centrifugation separation processes for separating the heterogeneous catalyst composition from the reaction mixture after producing the aldehyde.

[0092] The activity of heterogeneous catalyst composition, as quantified using reaction rate, is typically measured as the number of moles of product (aldehyde) per volume of catalyst solution per unit of time (generally scaled by the concentration of active metal) with units of gmols of aldehyde / L / hr / ppm Rh, for example. Other conventional measurements are in units of "turn-over number" or TON (units of hr’l), which is moles of aldehyde produced per moles of heterogeneous catalyst composition. The moles of heterogeneous catalyst composition are typically determined by measuring the amount of metal (e.g., rhodium) in ppm using Atomic Absorption or Inductively Coupled Plasma analysis) and comparison to the activity (reaction rate) of a fresh heterogeneous catalyst composition solution to calculate a "% Active" value.

[0093] In a preferred embodiment, the hydroformylation reaction mixtures employable herein includes any mixture derived from any corresponding hydroformylation process that contains at least some amount of the main ingredients or components, i.e., the aldehyde product, the heterogeneous catalyst composition, the heterogeneous catalyst precursor and an organic solubilizing agent, e.g., a polar solvent. It is to be understood that the hydroformylation reaction mixture compositions employable herein can and normally will contain minor amounts of additional ingredients such as those which have either been deliberately employed in the hydroformylation process or formed in situ during the process. Examples of such ingredients that can also be present include unreacted olefin stalling material, carbon monoxide and hydrogen gases, and in situ formed type products, such as saturated hydrocarbons and / or unreacted isomerized olefins corresponding to the olefin starting materials, and high boiling liquid aldehyde condensation byproducts, as well as other inert co-solvent, e.g., nonpolar solvent, type materials or hydrocarbon additives, if employed.

[0094] The substituted or unsubstituted olefin reactants that may be employed in the hydroformylation processes (and other suitable processes) of this disclosure include both optically active (prochiral and chiral) and non-optically active (achiral) olefinic unsaturated compounds containing from 2 to 40, preferably 2 to 20, carbon atoms. Such olefinic unsaturated compounds can be terminally or internally unsaturated and be of straight chain, branched chain or cyclic structures, as well as olefin mixtures, such as obtained from the oligomerization of propene, butene, isobutene,etc. (such as so called dimeric, trimeric or tetrameric propylene and the like, as disclosed, for example, in U.S. Pat. Nos. 4,518,809 and 4,528,433). Moreover, such olefin compounds may further contain one or more ethylenic unsaturated groups, and of course, mixtures of two or more different olefinic unsaturated compounds may be employed as the starting material if desired. For example, commercial alpha-olefins containing four or more carbon atoms may contain minor amounts of corresponding internal olefins and / or their corresponding saturated hydrocarbon and that such commercial olefins need not necessarily be purified from same prior to being reacted. Illustrative mixtures of olefinic stalling materials that can be employed in the hydroformylation reactions include, for example, mixed butenes, e.g., Raffinate I and II. Further such olefinic unsaturated compounds and the corresponding products derived therefrom may also contain one or more groups or substituents which do not unduly adversely affect the processes of this disclosure such as described, for example, in U.S. Pat. Nos. 3,527,809, 4,769,498 and the like.

[0095] The heterogeneous catalyst composition of the present disclosure may also be useful for the production of non-optically active aldehydes, by hydroformylating achiral alpha-olefins containing from. 2 to 30, preferably 2 to 20, carbon atoms, and achiral internal olefins containing from 2 to 20 carbon atoms as well as starting material mixtures of such alpha olefins and internal olefins.

[0096] Illustrative olefins include, for example, ethylene, propylene, 1 -butene, 1 -pentene, 1- hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1 -tetradecene, 1- pentadecene, 1 -hexadecene, 1 -heptadecene, 1 -octadecene, 1 -nonadecene, 1-eicosene, 2-butene, 2- methyl propene (isobutylene), 2-methylbutene, 2-pentene, 2-hexene, 3-hexane, 2-heptene, 2-octene, cyclohexane, propylene dimers, propylene trimers, propylene tetramers, butadiene, piperylene, isoprene, 2-ethyl-l -hexene, styrene, 4-methyl styrene, 4-isopropyl styrene, 4-tert-butyl styrene, alpha-methyl styrene, 4-tert-butyl-alpha- methyl styrene, 1,3-diisopropenylbenzene, 3-phenyl-l- propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-l -butene, and the like, as well as, 1,3-dienes, butadiene, pentenoic acids and salts, e.g., salts of 3- and 4-pentenoic acids, alkyl alkenoates, e.g., methyl pentenoate, alkenyl alkanoates, alkenyl alkyl ethers, alkenols, e.g., pentenols, alkenals, e.g., pentenals, and the like, such as allyl alcohol, allyl butyrate, hex-l-en-4-ol, oct-l-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinyl propionate, vinyl functional silanes, vinyl functional siloxanes, allyl propionate, methyl methacrylate, vinyl ethyl ether, vinyl methyl ether, allyl ethylether, n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, eugenol, iso-eugenol, safrole, iso- safrolc, 4-allylanisolc, indene, limonene, bcta-pincnc, dicyclopcntadicnc, cyclooctadicnc, camphene, linalool, and the like.

[0097] Illustrative prochiral and chiral olefins useful in the asymmetric hydroformylation processes (and other asymmetric processes) that can be employed to produce enantiomeric product mixtures that may be encompassed by in this disclosure include those represented by the formula:wherein R24, R25-R 26 and R27 are the same or different (provided R24 is different from R25 or R26is different from R27) and are selected from hydrogen; alkyl; substituted alkyl, the substitution being selected from dialkylamino such as benzylamino and dibenzylamino, alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy, halo, nitro, nitrile, thio, carbonyl, carboxamide, carboxaldehyde, carboxyl, carboxylic ester; aryl including phenyl; substituted aryl including phenyl, the substitution being selected from alkyl, amino including alkylamino and dialkylamino such as benzylamino and dibenzylamino, hydroxy, alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy, halo, nitrile, nitro, carboxyl, carboxaldehyde, carboxylic ester, carbonyl, and thio; acyloxy such as acetoxy; alkoxy such as methoxy and ethoxy; amino including alkylamino and dialkylamino such as benzylamino and dibenzylamino; acylamino and diacylamino such as acetylbenzylamino and diacetylamino; nitro; carbonyl; nitrile; carboxyl; carboxamide; carboxaldehyde; carboxylic ester; silane and substituted silane; siloxanes and substituted siloxanes; and alkylmercapto such as methylmercapto. It is understood that the prochiral and chiral olefins of this definition also include molecules of the above general formula where the R groups are connected to form ring compounds, e.g., 3-methyl-l -cyclohexane, and the like.

[0098] Illustrative optically active or prochiral olefinic compounds useful in asymmetric hydroformylation processes (and other asymmetric processes) include, for example, p- isobutylstyrene, 2-vinyl-6-methoxy-2-naphthylene, 3 -ethenylphenyl phenyl ketone, 4- ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl, 4-(l,3-dihydro-l-oxo-2H-isoindol-2- yl)styrene, 2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether, propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and the like. Other olefinic compounds includesubstituted aryl ethylenes as described, for example, in U.S. Pat. Nos. 4,329,507, 5,360,938 and 5,491,266, the disclosures of which arc incorporated herein by reference.

[0099] Illustrative vinyl functional silanes and vinyl functional siloxanes include trimethoxy(vinyl)silane, dimethoxy (methyl)(vinyl) silane, triethoxy (vinyl) silane, diethoxy(methyl)(vinyl)silane, hex-5-en- 1-yltrimethoxy silane, trimethyl(vinyl) silane, 1 , 1 , 1 ,3, 5,5,5- heptamethyl-3-vinyltrisiloxane, 1 , 1 ,3,3-tetramethyl- 1 ,3-divinyldisiloxane.

[0100] Illustrative of suitable substituted and unsubstituted olefinic starting materials include those permissible substituted and unsubstituted olefinic compounds described in Kirk- Othmer, Encyclopedia of Chemical Technology, Fifth Edition, 2004, the pertinent portions of which are incorporated herein by reference.

[0101] The hydroformylation processes involves the use of the heterogeneous catalyst composition of the present disclosure. Mixtures of such heterogeneous catalyst compositions can be employed if desired. The amount of the heterogeneous catalyst composition present in the reaction medium of a given hydroformylation process can include, for example, that minimum amount necessary to provide the given metal concentration desired to be employed and which will furnish the basis for at least the catalytic amount of metal necessary to catalyze the particular’ hydroformylation process. In general, metal, e.g., rhodium, concentrations in the range of from about 10 ppm to about 1000 ppm, calculated as rhodium, in the hydroformylation reaction medium should be sufficient for most processes, while it is generally preferred to employ from about 100 to 500 ppm of metal, e.g., rhodium, and more preferably from 250 to 400 ppm of metal, e.g., rhodium. Analytical techniques for measuring catalytic metal concentrations are well known to the skilled person, and include atomic absorption (AA), inductively coupled plasma (ICP) and X-ray fluorescence (XRF); A A is typically preferred.

[0102] In addition to the heterogeneous catalyst composition, free heterogeneous catalyst precursor (i.e., heterogeneous catalyst precursor that is not complexed with the Group VIII transition metal catalyst precursor compound to form the heterogeneous catalyst composition) may also be present in the hydroformylation reaction medium. The free heterogeneous catalyst precursor may correspond to any of the above-defined heterogeneous catalyst precursor. It is preferred that the free heterogeneous catalyst precursor be the same as the heterogeneous catalyst precursor used in forming the heterogeneous catalyst composition. However, such heterogeneous catalyst precursorneed not be the same in any given process. The hydroformylation process may involve from about 0.1 moles or less to about 100 moles or higher of free heterogeneous catalyst precursor, based on phosphorous content, per mole of metal in the hydroformylation reaction medium.

[0103] The reaction conditions of the hydroformylation processes may include any suitable type hydroformylation conditions known in the art for producing optically active and / or non- optically active aldehydes. For instance, the total gas pressure of hydrogen, carbon monoxide and olefin starting compound of the hydroformylation process may range from about 1 to 69,000 kilopascal (kPa). In general, however, it is preferred that the process be operated at a total gas pressure of hydrogen, carbon monoxide and olefin starting compound of less than 14,000 kPa and more preferably less than 3,400 kPa. The minimum total pressure is limited predominantly by the amount of reactants necessary to obtain a desired rate of reaction. More specifically, the carbon monoxide partial pressure of the hydroformylation process is preferably from 1 to 6,900 kPa, and more preferably from 21 to 5,500 kPa, while the hydrogen partial pressure is preferably from 34 to 3,400 kPa and more preferably from 69 to 2,100 kPa. In general, H2:CO molar ratio of gaseous hydrogen to carbon monoxide may range from about 1:10 to 100:1 or higher, the more preferred hydrogen to carbon monoxide molar ratio being from about 1:10 to about 10:1.

[0104] Further, the hydroformylation process, may be conducted at a reaction temperature from about -25 °C to about 200 °C. In general, hydroformylation reaction temperatures of about 50 °C to about 120 °C are preferred for all types of olefinic starting materials. When non-optically active aldehyde products are desired, achiral type olefin starting materials and organophosphorus ligands arc employed and when optically active aldehyde products arc desired prochiral or chiral type olefin starting materials and organophosphorus ligands are employed. It is to be also understood that the hydroformylation reaction conditions employed will be governed by the type of aldehyde product desired.

[0105] A solvent advantageously is employed in the hydroformylation process. Any suitable solvent that does not unduly interfere with the hydroformylation process can be used. The organic solvent may also contain dissolved water up to the saturation limit. When the metal of the heterogeneous catalyst composition is rhodium, it may be preferred to employ, as a primary solvent, aldehyde compounds corresponding to the aldehyde products desired to be produced and / or higher boiling aldehyde liquid condensation by-products, for example, as might be produced in situ duringthe hydroformylation process, as described for example in U.S. Pat. Nos. 4,148,830 and 4,247,486. Indeed, while one may employ, if desired, any suitable solvent at the start-up of a continuous process, the primary solvent will normally eventually comprise both aldehyde products and higher boiling aldehyde liquid condensation by-products ("heavies"), due to the nature of the continuous process. The amount of solvent need only be sufficient to provide the reaction medium with the desired amount of transition metal concentration. Typically, the amount of solvent ranges from about 5 percent to about 95 percent by weight, based on the total weight of the reaction fluid. Mixtures of two or more solvents may also be employed.

[0106] Illustrative non-optically active aldehyde products include e.g., propionaldehyde, n- butyraldehyde, iso-butyraldehyde, n- valeraldehyde, 2-methyl 1 -butyraldehyde, hexanal, hydroxy hexanal, 2-methyl valeraldehyde, helitanal, 2-methyl 1 -hexanal, octanal, 2-methyl 1- heptanal, nonanal, 2-methyl- 1 -octanal, 2-ethyl 1 -heptanal, 3-propyl 1 -hexanal, decanal, adipaldehyde, 2-methylglutaraldehyde, 2-methyladipaldehyde, 3-methyladipaldehyde, 3- hydroxypropionaldehyde, 6-hydroxyhexanal, alkenals, e.g., 2-, 3- and 4-pentenal, formylvaleric acids and salts, e.g., salts of 5-formylvaleric acid, alkyl 5-formylvalerate, 2-methyl- 1 -nonanal, undecanal, 2-methyl 1 -decanal, dodecanal, 2-methyl 1 -undecanal, tridecanal, 2-methyl 1 -tridecanal, 2-ethyl, 1 -dodecanal, 3-propyl- 1 -undecanal, pentadecanal, 2-methyl- 1 -tetradecanal, hexadecanal, 2- methyl-1 -pentadecanal, heptadecanal, 2-methyl- 1 -hexadecanal, octadecanal, 2-methyl- 1- heptadecanal, nonodecanal, 2-methyl- 1 -octadecanal, 2-ethyl 1 -heptadecanal, 3-propyl-l- hexadecanal, eicosanal, 2-methyl- 1 -nonadecanal, heneicosanal, 2-methyl- 1-eicosanal, tricosanal, 2- methyl-l-docosanal, tetracosanal, 2-methyl- 1 -tricosanal, pentacosanal, 2-methyl- 1-tetracosanal, 2- ethyl 1 -tricosanal, 3-propyl- 1-docosanal, heptacosanal, 2-methyl- 1-octacosanal, nonacosanal, 2- methyl-l-octacosanal, hentriacontanal, 2-methyl- 1-triacontanal, and the like.

[0107] Illustrative optically active aldehyde products include (enantiomeric) aldehyde compounds prepared by the asymmetric hydroformylation process such as, e.g. S-2-(p- isobutylphenyl)-propionaldehyde, S-2-(6-methoxy-2-naphthyl)propionaldehyde, S-2-(3- benzoylphenyl)-propionaldehyde, S-2-(p-thienoylphenyl)propionaldehyde, S-2-(3-fluoro-4- phenyl)phenylpropionaldehyde, S-2- [4-( 1 ,3-dihydro- 1 -oxo-2H-isoindol-2- yl)phenyl]propionaldehyde, S-2-(2-methylacetaldehyde)-5-benzoylthiophene and the like.

[0108] Illustrative aldehyde functional silanes / siloxanes products include 3- (trimcthoxysilyl)propanal, 3-(dimcthoxy(mcthyl)silyl)propanal, 3-(tricthoxysilyl)propanal, 3- (diethoxy(methyl)silyl)propanal, 7-(trimethoxysilyl)heptanal, 3-(trimethylsilyl)propanal, 3- (l,l,l,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal, 3,3'-(l,l,3,3-tetramethyldisiloxane-l,3- diyl)dipropanal.

[0109]

[0110] Illustrative of suitable substituted and unsubstituted aldehyde products include those permissible substituted and unsubstituted aldehyde compounds described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fifth Edition, 2004, the pertinent portions of which are incorporated herein by reference.

[0111] The aldehyde product mixtures may be extracted and separated from the other components of the crude reaction mixtures in which the aldehyde mixtures are separated by techniques as discussed herein. It is generally preferred to carry out the hydroformylation processes in a continuous manner. In general, continuous hydroformylation processes are well known in the art and may involve: (a) hydroformylating the olefinic starting material(s) with carbon monoxide and hydrogen in a liquid homogeneous reaction mixture comprising a polar solvent, the heterogeneous catalyst composition, free heterogeneous catalyst precursor, and optionally a nonpolar solvent; (b) maintaining reaction temperature and pressure conditions favorable to the hydroformylation of the olefinic starting material(s); (c) supplying make-up quantities of the olefinic starting material(s), carbon monoxide and hydrogen to the reaction medium as those reactants are used up; (d) mixing at least a portion of the reaction medium with a nonpolar solvent to extract the desired aldehyde hydroformylation product(s) from the reaction medium; and (e) recovering the desired aldehyde product(s) by, for example, phase separation.

[0112] At the conclusion of (or during) the hydroformylation process, the desired aldehydes may be recovered from the reaction mixtures. For instance, in a continuous liquid catalyst recycle process the portion of the liquid reaction mixture (containing the aldehyde product) can be removed from the reaction zone and passed to a separation zone where the desired aldehyde product can be extracted and separated via phase separation from the liquid reaction mixture, and further purified if desired. The remaining catalyst containing liquid reaction mixture may then be recycled back to the reaction zone as may if desired any other materials, e.g., unreacted olefin, together with allhydrogen and carbon monoxide dissolved in the liquid reaction after separation thereof from the aldehyde product.

[0113] The hydroformylation process of this disclosure may be carried out using one or more suitable reactors such as, for example, a fixed bed reactor, a tubular reactor, a venturi reactor, a bubble column reactor, a continuous stirred tank reactor (CSTR) or a slurry reactor, with the recycle of unconsumed starting materials. The optimum size and shape of the reactor will depend on the type of reactor used. The at least one reaction zone employed in this disclosure may be a single vessel or may comprise two or more discrete vessels in series or in parallel. The separation zone employed may be a single vessel or may comprise two or more discrete vessels. The buffer treatment zone employed in this disclosure may be a single vessel or may comprise two or more discreet vessels. The reaction zone(s) and separation zone(s) employed herein may exist in the same vessel or in different vessels. For example, reactive separation techniques such as reactive distillation, reactive membrane separation, and the like, may occur in the reaction zone(s).

[0114] The materials of construction employed should be substantially inert to the starting materials during the reaction and the fabrication of the equipment should be able to withstand the reaction temperatures and pressures. Means to introduce and / or adjust the quantity of starling materials or ingredients introduced continuously into the reaction zone during the course of the reaction can be conveniently utilized in the process especially to maintain the desired molar’ ratio of the starting materials. The starting materials and / or recycled olefin may be added to each or all the reaction zones in series.

[0115] The hydroformylation process may be conducted in either glass lined, stainless steel or similar type reaction equipment. The reaction zone may be fitted with one or more internal and / or external heat exchanger(s) in order to control undue temperature fluctuations, or to prevent any possible "runaway" reaction temperatures.

[0116] The hydroformylation process of this disclosure may be conducted in one or more steps or stages. The exact number of reaction steps or stages will be governed by the best compromise between capital costs and achieving high catalyst selectivity, activity, lifetime and ease of operability, as well as the intrinsic reactivity of the starting materials in question and the stability of the starting materials and the desired reaction product to the reaction conditions.

[0117] For the various embodiments, the present disclosure further includes separating the heterogeneous catalyst composition from the reaction mixture after producing the aldehyde using one of a decanting, filtration process, a membrane separation process or a centrifuge separation process. A catalyst basket can also be used to hold the heterogeneous catalyst composition during the reaction, which can then be lifted from the reaction mixture directly. In addition, if the substrate, products, and solvent of the reaction mixture are sufficiently volatile, the heterogeneous catalyst composition can be recycled directly in the reactor. For example, this could be done by purging the reactor of syngas and then applying a vacuum sufficient to evaporate the liquid components, which would be collected in a N2 trap. Alternatively, the heterogeneous catalyst composition could be filtered and a backflush of fresh reagents / solvents could be used to reintroduce the heterogeneous catalyst composition back into the reactor, Such techniques would allow for the heterogeneous catalyst composition to be isolated for recycling without exposure to air or water.

[0118] The heterogeneous catalyst composition recovered from the reaction mixture can be recycled by a series of trituration and soaking steps. For example, the heterogeneous catalyst composition can be triturated several times (e.g., three times) with a wash solvent (fresh each time) at room temperature (e.g., 23 °C) followed by a soak in the wash solvent for approximately one hour (h). The wash solvent is then replaced with fresh wash solvent and the heterogeneous catalyst composition soaked again for 1 h. The heterogeneous catalyst composition is then triturated three time with hexanes (CgH 14), then soaked once in fresh hexanes for 1 h, and then finally the solvent is decanted and the solids dried in vacuo to yield the recycled heterogeneous catalyst composition. Suitable wash solvents include toluene or diethyl ether. The use of other wash solvents and organic solvents besides hexanes is also possible. In addition, soak times can range from thirty (30) minutes to several days. A soak time of one hour, however, is typically sufficient.EXAMPLESMaterials

[0119] The following materials were used in the following Examples (EX) and Comparative Examples (CE). All materials were purchased from the following companies and used as received, unless otherwise noted.

[0120] Rh(acac)(CO)2, 1 -octene, hydrazine monohydrate, NaNCh, Glacial AcOH, Boroscillatc glass beads, and 1-chlorobutanc each from Sigma- Aldrich®. Hydrazine monohydratc, 2-norbomene and 1-nonanal each from TCI® (Tokyo Chemical Industry). (R,R)-(-)-Norphos (Norphos) and AICI3 from Strem Chemicals. DMSO-defrom Cambridge Isotope Laboratories, Inc. Synthesis gas (1:1 mixture of H2 / CO) from AirGas®. A.A-Dimcthylformamidc (DMF), N’N- diethylformamide (DEF), ethanol (EtOH), methanol (MeOH), dichloromethane (DCM), diethyl ether (Et20), and anhydrous toluene from Sigma- Aldrich® were of standard grade and used as received without further purification, except where indicated. DI Water (H2O). 1-octadecene (Cl 8) from Beantown Chemical. 4-Cyanobenzoic acid from Apollo Scientific. Silicon carbide (SiC) from Fisher Scientific.

[0121] Dry, deaerated MeOH, DME, and DCM were obtained by passing the solvent through two silica columns in a Glass Contour Solvent System and degassing with a flow of argon gas for thirty minutes (min), followed by three freeze-pump-thaw cycles. All other commercial reagents were used as received without further purification.

[0122] All BET Surface Area measurements for the following examples were conducted using an ASAP 2020 adsorption analyzer (Micromeritics®) with nitrogen used as the analysis gas.

[0123] PXRD diffractograms measurements for the following examples were conducted using a Bruker Advance II diffractometer equipped with 9 / 29 Bragg-Brentano geometry and Ni- filtered Cu-Ka radiation (Kai = 1.5406 A). The tube voltage and current were 40 kV and 40 mA, respectively. Samples for PXRD were prepared by placing a thin layer of the appropriate material on a zero-background silicon crystal plate.

[0124] All1H NMR measurements for the following examples were conducted using a Avance NEO 400 MHz NMR with DMSO-de as the solvent. All solid-state31P NMR for the following examples were conducted using a cross polarization / magic angle spinning (CPMAS) method using a Avance NEO 500 MHz NMR with a 5mm 3 IP TBI probe.

[0125] As used herein, the @ symbol represents the covalent bonds used to join the identified species onto the MOF framework.

[0126] A series of crystalline porous MOFs AlTz-68-Cx composed of organic tetrazinebased building blocks connected through aluminum clusters, were synthesized according to the following procedure.Synthesis of Crystalline Porous MOFs AlTz-68-Cx4,4’-(l,2,4,5-tetrazine-3,6-diyl)dibenzoic acid (HiTzDB)

[0127] To a 100-ml round bottom flask (RBF) were added 4-cyanobenzoic acid (6.0 g, 40 mmol) and 1” stir bar. 20 ml of hydrazine monohydrate (64-65%) was diluted with 20 ml distilled water and directly added to the RBF. The RBF was connected to a reflux condenser, and the reaction stirred at 85 °C for 4 h. The reaction was then cooled down to room temperature (23 °C), and the yellow solid was centrifuged and washed with water (3 x 50 ml). The solid was added into a 100 ml RBF with 15 ml water followed by addition of 60 ml acetic acid. The flask was cooled down to 0 °C using an ice bath. NaNCE (8.2 g, 120 mmol) was dissolved in 15 ml water and then was added dropwise to the reaction using an addition funnel. The reaction was stirred for 3 h at 0 °C. The purple solids were collected by centrifuged and washed with water (4 x 50 ml), EtOH (3 x 50 ml) and diethyl ether (3 x 50 ml). The solid was transferred into a glass vial and dried by heating at 70 °C while purging with a slow flow of N2 to yield pure FhTzDB (3.1 g purple solid, 9.6 mmol, 48% yield) ’H NMR (400 MHz, DMSO-d6): 8 8.55 (d, 4 H, CH-phenyl); 8 8.19 (d, 4 H, CH-phenyl) (Fig. S6.1)Disordered AlTz-68

[0128] To a 100-ml RBF were added finely grinded H2TZDB (0.576 g, 0.17 mmol) and 1” stir bar. AICI3 (0.313 g, 2.35 mmol) was directly added to the RBF followed by addition of 50 ml diethyl formamide (DEF). The RBF was capped with a glass stopper and the reaction stirred at 120 °C for 48 h. The reaction was cooled down to room temperature and the pink-colored solids were collected. The material was then washed with hot DMF (3 x 100 ml, 120 °C for 1 h in glass jar in an oven) and stored in DMF for subsequent reactions.AlTz-68-04

[0129] The following is a test yet to be completed. To a 100-ml RBF were charged with a mixture of 1-tetradecene (C14, 20 ml) and Et20 (30 ml) along with a 2” stir bar. Disordered AlTz- 68 (~ 175 mg) was separated from DMF and added to the RBF. The suspension stirred for 30 min. at 30 °C. The remaining MOF particles were centrifuged and thoroughly rinsed with Et2O (4 x 30ml) and dried at 40 °C overnight. The resulting AlTz-68-C14 was activated by heating under high vacuum at 120 °C overnight ( mg pink solids, ~ % yield) BET Surface Area: m2 / g.AlTz-68-C16

[0130] The following is a test yet to be completed. To a 100-ml RBF were charged with a mixture of 1 -hexadecene (Cl 6, 20 ml) and Et^O (30 ml) along with a 2” stir bar. Disordered AlTz- 68 (~ 175 mg) was separated from DMF and added to the RBF. The suspension stirred for 45 min. at 30 °C. The remaining MOF particles were centrifuged and thoroughly rinsed with EtiO (4 x 30 ml) and dried at 40 °C overnight. The resulting AlTz-68-C16 was activated by heating under high vacuum at 120 °C overnight ( mg pink solids, ~ % yield) BET Surface Area: nr / g.AlTz-68-C18

[0131] To a 100-ml RBF were charged with a mixture of 1 -octadecene (Cl 8, 20 ml) and Et2O (30 ml) along with a 2” stir bar. Disordered AlTz-68 (~ 175 mg) was separated from DMF and added to the RBF. The suspension stirred for 1 h at 30 °C. The remaining MOF particles were centrifuged and thoroughly rinsed with EtiO (4 x 30 ml) and dried at 40 °C overnight. The resulting AlTz-68-C18 was activated by heating under high vacuum at 120 °C overnight (150 mg pink solids, ~80 % yield) BET Surface Area: 1726 m2 / g.

[0132] The hydrophobic nature of the above MOFs (AlTz-68-C14, AlTz-68-C16, AlTz-68-C18, referred to herein collectively as AlTz-68-Cx) stems from the long chain alkyl hydrocarbons (e.g., produced using 1 -tetradecene, C14; 1-hexadecene, C16; 1-octadecene, C18), chemically grafted onto exterior tetrazine linkers through tetrazine-click grafting, which provides varying degrees of hydrophobicity to the MOF particles. The degree of hydrophobicity may be adjusted through the reaction time used for each of the long chain alkyl hydrocarbons, where grafting the hydrocarbons onto MOF required a balance of reaction times in order to minimize, or prevent, the pores from clogging and the subsequent loss of porosity arising from time-dependent diffusion of hydrocarbons into pores and clicking onto internal linkers. Conversely, providing a lowered reaction time may not have allowed for enough of the hydrocarbon molecules to click and coat the MOF particles, leading to poor hydrophobicity. To accomplish a proper synthesis of AlTz-68-C14 andAlTz-68-C 16, the reaction time was adjusted and lowered down to 45 min and 0.5 hours, respectively. Comparison of BET surface area and PXRD diffractograms from the nonhydrophobic parent MOF (AlTz-68), before and after click reaction, as seen in FIGS. 1A-1F, reveals all three MOFs (AlTz-68-C14, AlTz-68-C16, AlTz-68-C18) maintained their porosity and crystallinity upon hydrophobication process, overall, creating highly porous and crystalline platforms for embedding catalysts.Grafting of Phosphorus Ligands and Metallation to Form Heterogeneous Catalysts

[0133] Unprecedently, the modularity of the tetrazine click- grafting technique also enables chemical installation of phosphorus ligands onto AlTz-68-Cx series for which a dienophile-tagged phosphorus ligand was employed. The norbomyl derivative ( / ?, / ?)-( )- Norphos was targeted due to the high activity of norbomenes for the tetrazine click reaction, and for its commercial availability.General Procedure to Prepare Heterogeneous Catalysts Rh(NP)(NB)@AlTz-68-Cx[00134J Installation of phosphorus ligand onto frameworks via tetrazine click-grafting was accomplished by soaking samples of activated AlTz-68-Cx MOF (100 mg) in a DCM solution (3 ml) of 0.023 mmol) in a 20-ml glass vial under N2 at60 °C. The reaction solution contained 0.1 equivalent of dienophile versus total tetrazine sites. After 48 h with stirring, the reaction solution was decanted and the MOF was washed by soaking in fresh DCM (2 ml) for at least 1 h. The MOF samples were then treated with excess 2-norbomene (500 mg, 0.46 mmol) in DCM (~20 equiv. versus tetrazine) under N2 at 60 °C to block unfunctionalized tetrazine sites. Upon immersing the MOF in a solution of excess norbornene, bubbles of N2 immediately began to evolve from the MOF as a byproduct of the tetrazine click reaction. After 24 h of stirring, the phosphorus-grafted MOF was washed with DCM (2 x 10 ml). Qualitatively, the tetrazine MOFs undergo a distinct color change from pink to yellow upon click-grafting, consistent with the color change observed for molecular tetrazines upon click reaction. Rh metalation was then achieved by immersing the MOF in a fresh DCM solution (1 ml) containing Rh(acac)(CO)2 (6 mg, 0.023 mmol). After stirring for 24 h at room temperature, the final catalyst was washed with DCM (2 x 10ml) and then diethyl ether (2 x 10 ml). The resulting Rh(NP)(NB)@AlTz-68-Cx) was activated under vacuum (~80 mg yellow solids, 75% yield) Crystallinity of the MOF was maintained after click-grafting, as determined by PXRD. Outside of the expected losses due to partial pore filling, the click-grafted MOFs also maintained high surface areas, as determined by N2 gas sorption (FIG. 1).

[0135] Characterization by31P-CPMAS of the non-metallated, phosphorus containing material reveals a clear sharp signal which correspond to the free -base phosphine. Upon Rh incorporation, the phosphorus ligand is found to be accessible to species in the pores, resulting in an unambiguous downfield shift of the 31P-CPMAS signal consistent with coordination of the phosphorus to a metal (FIG. 2).Hydroformylation Catalysts

[0136] The MOF-supported Rh phosphine catalyst Rh(Norphos)(acac)@AlTz-68- C18, was investigated as a catalyst for the hydroformylation of 1-octene to 1-nonanal (and regioisomers), as illustrated:+ isomers

[0137] The Rh-containing MOF catalyst was found to be able to be stored under inert atmosphere and for months as a dried powder.General Procedure for Batch Hydroformylation with 1-Octene

[0138] Under inert atmosphere, a Parr reactor (Parr Instrument Company, Series 4790 pressure vessel systems; 25 mL capacity vessel with flat PTFE flat gasket for temperatures up to 350 °C) was charged with the target catalyst (20 mg), 1-octene (5 ml, 31.8 mmol) and a 1” stir bar. The reactor was sealed, placed on top of a stirring plate and connected to gas manifold system preevacuated and backfilled with N2 three times. The Parr reactor was then open to the manifold and pressurized with 400 psig of synthesis gas (1:1 H2 / CO). The reactor was then closed to the manifold and the heating mantle was set to 100 °C (Pan- Instrument Company, Model 4838) and stirred at300 rpm for 4 h. At the end of the reaction, the reactor was removed from the manifold and carefully placed inside an ice-bath and cooled to room temperature. After cooling process, the reactor was again connected to the manifold and carefully depressurized using the manifold lines and then purged with N2 to remove remaining syngas from the headspace. The reactor was opened and 1 -chlorobutane (0.1 ml, 0.95 mmol) was added as internal standard. A sample (0.2 ml) of the mixture was then diluted with 5 ml toluene, filtered to remove solid catalyst particles, and analyzed by GCMS (Agilent 7890B with a 5977A MSD and a J&W DB-5ms Ultra Inert column), averaged over three samples.AnalysisComments on Results of Tables 1-3

[0139] A completely new and upgraded catalytic performance was observed where two major developments are established, addressing the challenges of current MOF-based catalysts. For the first development, Rh(Norphos)(acac)@AlTz-68-C18 achieves (Table 1) high oxo reactivity in terms of yield, TON, and TOF. It displays an improved catalytic performance in comparison to other MOF counterparts in the literature (Table 3) impregnated with homogeneous catalyst. It also exhibits an improved performance to homogeneous transition metal complexes, including the molecular [Rh(Norphos)(acac)] analogue generated in situ. While the material exhibits a lower oxo reactivity compared to when the molecular analogue is first formed (Table 2), it is not prone to deactivation that affects the homogeneous analogue’s oxo activity within a day of being prepared (Table 2). The hydrophobic coating is found to lead to the observed enhancement, as absence of the C18 coating results in a near 8-fold decrease in activity (Table 2, Entry 4). Furthermore, olefin isomerization, a prominent chain walking side reaction initiated by rapid hydrogen atom exchange over Rh-sites, is significantly suppressed down to 3%, which is not observed in with homogenous [Rh(Norphos)(acac)] (Table 2) This sets the lowest isomerization record among similar Rh- phosphine heterogeneous catalysts.Table 1 - Hydroformylation of 1 -octene by molecular Rh(acac)Norphos, superhydrophobicRh(acac)Norphos@AlTz-68-C18 and non-hydrophobic Rh(acac)Norphos@AlTz-68CHO C=C yield isomerCatalyst S / Ca(%)byield (%)en / iso TONdTOFCF A ouz N? K e 11800 13.3 34.3 3.1 1569 392Rh(acac)NorphoseEX 1Rh(acac)Norphos 11796 40.4 3.3 1.1 3922 980@AlTz-68-C18EX 2 Rh(acac)Norphos 35400 16.0 0.9 1.1 5254 1314@AlTz-68-C18CE B Rh(acac)Norphos 35400 1.0 2.2 1.0 664 166@AlTz-68aS / C: pmol(substrate) / pmol(Rh)b%CHO: yield of 1 -octene to aldehyde, as pmol(aldehyde) / pmol(total)c%C=C: yield of 1 -octene to alkene isomers, as pmol(isomers) / pmol(total)dTON and TOF calculated with respect to aldehyde production: TON = pmol CHO / pmol Rh, TOF = TON / 4 hePrepared in situ (solvent DCM or toluene) and stored for one day under inert atmosphereTable 2. Hydroformylation of 1 -octene by molecular Rh(acac)Norphos, superhydrophobicRh(acac)Norphos@AlTz-68-C18 and non-hydrophobic Rh(acac)Norphos@AlTz-68CHO yield C=C isomerCatalyst S / Ca(%)” yield (%)cn / iso TONdTOCF CXXT K e 35400 55.6 17.7 1.0 19680 4920Rh(acac)NorphoseCF D M K e 11800 81.5 11.2 1.1 9617 2404Rh(acac)Norphose“J K f 11800 13.3 34.3 3.1 1569 392Rh(acac)NorphosrEX 3 Rh(acac)Norphos 11796 40.4 3.3 1.1 3922 980@AlTz-68-C18EX 4 Rh(acac)Norphos 35400 16.0 0.9 1.1 5254 1314@AlTz-68-C18EX 5 Rh(acac)Norphos 35400 1.0 2.2 1.0 664 166@AlTz-68aS / C: pmol(substrate) / pmol(Rh)b%CHO: yield of 1 -octene to aldehyde, as pmol(aldehyde) / pmol( total)c%C=C: yield of 1-octene to alkene isomers, as pmol(isomers) / pmol(total)dTON and TOF calculated with respect to aldehyde production: TON = pmol CHO I pmol Rh, TOF- TON / 4 hTrepared in situ (solvent DCM or toluene) and immediately added to reactionfPrepared in situ (solvent DCM or toluene) and stored for one day under inert atmosphereTable 3 - MOF-Catalyzed HydroformylationCatalyst Substrate S / C %CHQan / iso %C=C isome? TON" TOF (h’1)'Procedure for Fixed Bed Flow Hydroformylation with 1 -octene

[0140] The fixed bed reactor was prepared using a 3 ft *4” diameter stainless-steel tubing equipped with a thermocouple fixed inside the tubing. Borosilicate glass beads (dia. 1 mm) was used to fill the tubing to just above the thermocouple. Then under inert atmosphere, catalyst (20 mg) was diluted 60 times with silicon carbide (1.2 g SiC, 320 grit), which was then tightly packed on top of the temperature controller and secured between two pieces of quartz wool. The reactor was sealed and secured to the stainless-steel flow setup pre-pressurized with N2 gas (400-450 psig) using a mass flow controller (MFC, Brooks Instrument, 60 ml / min). The reactor was pressurized under N2-gas, then 10-15 ml of the 1 -octene was injected to the reactor using a syringe pump (Chemyx Fusion 6000-X, 0.1 ml / min). The pump was stopped, the reactor was closed from both ends and was kept under substrate and N2 overnight, to properly soak the active catalyst sites with substrate. On the following day, the reactor was heated to 100 °C (Applied Test Systems Series 3210 Furnace, Digi-Sense Standard Temperature Controller) and injected with a continuous flow of substrate (0.03 ml / min). Upon reaching stable temperature and gas flow, N2 flow was stopped and the system was pressurized with syngas (400-450 psig, 60 ml / min.). The entire liquid outflow was collected between every 6-16 h. A sample (0.2 ml) of the outflow was then diluted with 5 ml toluene with 25 pl 1 -chlorobutane, filtered to remove any solids particles, and submitted for GCMS analysis averaged over three samples. After 48 h, the syngas was closed and the 1 -octene flow was stopped. The reactor was pressurized with N2 to dry the catalyst and purge any remaining syngas. The reactor was then re-pressurized with syngas and re-flowed with 1-octene for an additional 24 h. The results are shown in FIG. 4, and the following comments are provided. To demonstrate the use of the described catalyst in a heterogeneous system, a model fixed bed reactor system was designed and implemented. Under a constant flow (0.03 ml / min) of 1-octene substrate, the catalyst displays good aldehyde activity and minimal amount of isomerization, comparable to the batch reactions. The activity is maintained over 48 h of constant flow and the stability is further demonstrated during recycling of the catalyst for an additional 24 h of reaction time without noticeable loss in activity.

Claims

What is claimed is:

1. A crystalline porous metal-organic framework (MOF) comprising: a plurality of non-catalytic metal ions; a plurality of linkers formed from a compound of Formula I:Formula I wherein each of R and R’ is independently selected from:wherein each of Rj and R2 are independently H, C1to C3alkyl, -F, -Cl, -Br, -I, or -CF3; wherein each of R3and R4 are independently H or C ] to C3alkyl, wherein R3andR4 can form a bridge structure;X is selected from O and S;L] and L2 are each selected from the group:wherein each of R5, R8and R7 are independently selected from -H -ORJQ, -COORy , - NR12 -F, -Cl, -Br, -I, or -CF3, wherein Rj(p Rj ] and Rj2 are each independently selected from -H or Ci to C3alkyl; wherein each R8and R9are independently selected from -H, -OH, -COOH, or -NH2; andWhat is claimed is:

1. A crystalline porous metal-organic framework (MOF) comprising: a plurality of non-catalytic metal ions; a plurality of linkers formed from a compound of Formula I:Formula I wherein each of R and R’ is independently selected from:wherein each of Rj and R2 are independently H, C1to C3alkyl, -F, -Cl, -Br, -I, or -CF3; wherein each of R3and R4 are independently H or C1to C3alkyl, wherein R3andR4 can form a bridge structure;X is selected from O and S;L1and L2are each selected from the group:wherein each of R5, R8and R7 are independently selected from -H -OR10, -COOR11 - NR12 -F, -Cl, -Br, -I, or -CF3, wherein R10, R1 1and R12are each independently selected from -H or C1 to C3alkyl; wherein each R8and R9are independently selected from -H, -OH, -COOH, or -NH2; andA 1 and A2 are either C or N; and a plurality of C12to C20alkyl moieties, wherein the plurality of non-catalytic metal ions and the plurality of C12to C20alkyl moieties coordinate with the plurality of linkers to form the crystalline porous MOF.

2. The crystalline porous MOF of claim 1, wherein each of R and R’ is:

3. The crystalline porous MOF of claim 2, wherein R1is -H, -F or -CF3and R2is -H.

4. The crystalline porous MOF of claim 2, wherein I4 is5. The crystalline porous MOF of claim 2, wherein I4 is -COOH, R1is -F and R2is -H.

6. The crystalline porous MOF of claim 1, wherein each of R and R’ is:

7. The crystalline porous MOF of claim 1, wherein each of R and R’ is:

8. The crystalline porous MOF of claim 7, wherein R1is H.

9. The crystalline porous MOF of any one of claims 1-8, wherein the plurality of non- catalytic metal ions are selected from the group consisting of nickel, magnesium, copper, cobalt, zirconium, iron, zinc, vanadium, aluminum and combinations thereof.

10. The crystalline porous MOF of any one of claims 1-8, wherein the plurality of non- catalytic metal ions are nickel or magnesium.

11. The crystalline porous MOF of any one of claims 1-10, wherein the plurality of C12to C20alkyl moieties is selected from the group consisting of a C14alkyl moiety, a C16alkyl moiety, a C18alkyl moiety and combinations thereof.

12. The crystalline porous MOF of any one of claims 1-10, wherein the plurality of C12to C20alkyl moictics is a C18alkyl moiety.

13. A heterogeneous catalyst precursor, comprising: a reaction product of the crystalline porous MOF of any one of claims 1-12 and a phosphorous ligand of Formula II:Formula II, to form the heterogeneous catalyst precursor of Formula III:Formula III; or a phosphorous ligand of Formula IV:Formula IV, to form the heterogeneous catalyst precursor of Formula V:a phosphorous ligand of Formula VI:Formula VI; to form the heterogeneous catalyst precursor of Formula VII:a phosphorous ligand of Formula VIII:Formula VIII; orFormula C and an amine catalyst to form the heterogeneous catalyst precursor of Formula IX:Formula IX; or a phosphorous ligand of Formula D:wherein R16and R17are each independently -H and C1to C3alkyl; and wherein R13- R1a5re each independently selected from -H, C1to C30alkyl and at least one of:wherein n, m, and q are either 0 or 1, wherein (n,m,q) is either (1,0,0), (1,1,0), (0,0,1), (0,1,1) or (1,1,1); wherein each of R18 through R2iare selected from C5-C10 aryl, C1-C4 alkyl or -N(R22)2’ wherein R22 is selected from -H or C1 to C3alkyl; and wherein each of R23 is selected from C5-C4Q aryl, C4-C4 alkyl, -OR22 or -N(R22)2’ where R22 is selected from -H or C | to C3alkyl.

14. The heterogeneous catalyst precursor of claim 13, wherein the heterogeneous catalyst precursor is of Formula III and R 13 and R 14 are each diphenylphosphine.

15. The heterogeneous catalyst precursor of claim 13, wherein R13 is H and R14 is PPh2-16. A heterogeneous catalyst composition for hydroformylation of olefins, comprising: a reaction product of the heterogeneous catalyst precursor of any one of claims 13-15 with a Group VIII transition metal catalyst precursor compound.

17. The heterogeneous catalyst composition of claim 16, wherein the Group VIII transition metal catalyst precursor compound is of Formula X:wherein the M is selected from the group consisting of rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fc), nickel (Ni), palladium (Pd), platinum (Pt), and osmium (Os);L1, L2and L3are each independently selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, oxygen, boron, fluoride, bromide, iodide, nitrate, acetate, octanoate, 2-ethylhexanoate, triphenylphosphine (TPP), and acetylacetonate (Ac Ac); w is an integer from 1 to 6; and x, y and z are each independently an integer from 0 to 5 wherein the sum of x, y, and z is at least 1.0.

18. The heterogeneous catalyst of claim 17, wherein the transition metal catalyst of Formula X is selected from the group consisting of Rh(O2CsH7)(CO)2, RI12O3, Rh4(CO)i2, Rh6(CO)i6, Rh(NO3)3, bis(norbornadiene)rhodium(I) tetrafluoroborate and bis(l,5- cy clooctadiene)rhodium(I) tetrafluoroborate .

19. The heterogeneous catalyst of claim 16, wherein the heterogeneous catalyst precursor is provided in a molar excess, based on phosphorous content, relative the Group VIII transition metal catalyst precursor compound.

20. A method of forming a heterogeneous catalyst, comprising: reacting a compound of Formula I of any one of claims 1-12 with a metal acetate to form a crystalline porous metal-organic framework (MOF); reacting a phosphorous ligand of any one of Formula II, Formula IV, Formula VI or Formula VIII of any one of claims 13-15 with the crystalline porous MOF in a reaction to form a heterogeneous catalyst precursor of Formula III, Formula V, Formula VII or Formula IX, respectively, of any one of claims 13-15; and reacting the Group VIII transition metal catalyst precursor compound of any one of claims 16-19 with the heterogeneous catalyst precursor of any one of claims 13-15 to form the heterogeneous catalyst.

21. A method of producing an aldehyde, comprising: providing a reaction mixture of an C3to C12 olefin, synthesis gas and the heterogeneous catalyst of any one of claims 16-19; and reacting the C3to C12 olefin with synthesis gas in the presence of the heterogeneous catalyst in a hydroformylation process to produce the aldehyde.

22. The method of claim 21, wherein C3to C12 olefin includes a vinyl functional silane or a vinyl functional siloxane.

23. The method of claim 21, wherein the hydroformylation process is conducted in a fixed bed process.

24. The method of claim 21, further including separating the heterogeneous catalyst from the reaction mixture after producing the aldehyde using one of a filtration process, a membrane separation process or a centrifuge separation process.

25. The method of claim 24, wherein separating the heterogeneous catalyst includes: purging synthesis gas from reaction mixture; and drying the heterogeneous catalyst under vacuum to separate the heterogeneous catalyst from the reaction mixture.

26. The method of claim 24, further including soaking the heterogeneous catalyst with a wash solvent prior to drying the heterogeneous catalyst.

Images