Synthesis of carbonylation catalyst using an alkylaluminum reduction

Abstract

A method including contacting a cobalt salt comprising one or more of a cobalt halide or ester with a trialkylaluminum or halodialkylaluminum in a coordinating compound and / or an inert solvent to form a solution; contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of from about 25°C to about 100°C under conditions to form cobalt carbonyl: and contacting the cobalt carbonyl with a porphyrin metal halide or alkyl and a coordinating compound, and optionally an inert solvent, under conditions to form a complex of a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.

Description

SYNTHESIS OF CARBONYLATION CATALYST USING AN ALKYLALUMINUM REDUCTIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and benefit of U.S. Provisional Application No. 63 / 521 ,443 filed on June 16, 2023, which is incorporated herein by reference in its entirety.Field

[0002] The present disclosure relates to a method for preparing carbonylation catalysts from ligand complexes, metalation compounds, and metal carbonyls.Background

[0003] Carbonylation is a process that can be used to react carbon monoxide and an epoxide to make a lactone. In some cases, additional steps are taken to react the lactones to make polymers. These lactones or polymers thereof are often used as plastics and disinfectants. When making these lactones, a carbonylation catalyst is used to optimize the efficiency of the reaction to produce lactones at competitive prices. Carbonylation catalysts are expensive, and thus, new techniques to synthesize the carbonylation catalysts from simple components are needed. Some catalysts have been made using a variety of ligands. For example, see US Patent Number 6,852,865. However, the process to synthesize the carbonylation catalyst from these ligands can utilize many synthetic and purification steps.

[0004] In the existing catalyst synthesis procedure, (TPP)AIEt is reacted with Co2(CO)8, which is pre-formed in a high-pressure, high-temperature reaction, to form the standard catalyst [(TPP)AI(THF)2][Co(CO)4], A problem with the current synthetic procedure is that Co2(CO)8 is not widely available, its synthesis requires high temperature (200 oC) and CO pressures (>1800 psi), and its high instability makes it difficult to isolate and handle (air-sensitive, loses CO easily and decomposes to Co4(CO)12 or Co metal, stored below 0 oC).

[0005] Other methods have been reported to form Co2(CO)8 and other cobalt carbonyls under less harsh conditions. The resulting cobalt carbonyl is generally not isolated or characterized and is used in situ for a catalytic reaction. Conditions that have been replicated have had low yield (< 40%). In some cases, a sulphurated promoter is required. Other downsides include the use of highly toxic reagents (KCN) or byproducts that would hinder catalyst formation (BH3, tAmOH). Anew report (L. He, J.-C. Yang, T.-T. Song, Y. Liu, X.-B. Lu, Eur. J. Inorg. Chem. 2022, e202200496; Carbonylative Ring Expansion of Epoxides to f>- Lactones Using Inorganic Salt as Catalytic Species Piecursor - He - European Journal of Inorganic Chemistry - Wiley Online Library) showed that epoxides can be converted to lactones using simple CoBr2, Mn, and a Lewis acid complex ((salph)CrCI). The main drawbacks are that high amounts of polymer are formed and high loadings of catalyst, reducing agent and cobalt salts are required. To mitigate polymer formation, the reaction can be run at lower temperatures (50 oC), but this leads to significantly lower reaction rates of carbonylation. Methods have been developed to form carbonylation catalysts using metal reducing agents, like Zn or Mn, to reduce cobalt salts prior to carbonylation so that the reducing agent and other insoluble materials can be removed. One drawback of this method is that the metal salt byproducts (MnCI2, ZnCI2) can be difficult to completely remove from the final catalyst product. At sufficient levels, these salts can polymerize beta-propiolactone during carbonylation.

[0006] Accordingly, what is needed are techniques to form carbonylation catalysts that do not require the isolation of Co2(CO)8 or high pressure and temperature conditions and that form no new byproducts from their formation that can transfer into carbonylation or polymerization and inhibit these processes.Summary

[0007] Disclosed herein is a method including contacting a cobalt salt comprising one or more of a cobalt halide and / or ester with a trialkylaluminum or halodialkylaluminum in a coordinating compound and / or an inert solvent to form a solution; contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of from about 25 °C to about 100 °C under conditions to form cobalt carbonyl: and contacting the cobalt carbonyl with a porphyrin metal halide or alkyl and a coordinating compound, and optionally an inert solvent, under conditions to form a complex of a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.

[0008] The molar ratio of the trialkylaluminum or halodialkylaluminum to the cobalt salt is 2.0 to 1 .0 or greater. The inert solvent may be a non-polar ether, aromatic solvent, or alkane. The coordinating compound and / or an inert solvent may be diethyl ether, tetrahydrofuran, or toluene, or heptane. The porphyrin metal halide or alkyl and cobalt carbonyl may be contacted such that there is a molar excess of porphyrin metal halide or alkyl. The porphyrin metal halide or alkyl and cobalt carbonyl may be contacted at a molar ratio of 2.0. :1 or greater. The molar ratio or greater of the coordinating compound may be contacted with porphyrin metal halide or alkyl.

[0009] Disclosed herein is a method including contacting a trialkylaluminum or halodialkylaluminum with a porphyrin ligand and in inert solvent to form a solution containing aporphyrin metal halide or alkyl; b) contacting the solution of with a cobalt salt comprising one or more of a cobalt halide and / or ester to make a formed solution ; and, contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of about 10 °C to about 120 °C in the presence of a coordinating compound under conditions to form a complex containing a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.

[0010] The molar ratio of the trialkylaluminum or halodialkylaluminum to cobalt salt may be 3.0:1 .0 or greater. The inert solvent may be an alkane or aromatic solvent. The inert solvent may be toluene, heptane, or a hexane. An equivalent excess of the trialkylaluminum or halodialkylaluminum may be contacted with the tetraphenylporphyrin. The trialkylaluminum or halodialkylaluminum may be contacted with the tetraphenylporphyrin at a molar ratio of about 3.0:1 .0 or greater. An equivalent excess of the coordinating compound may be contacted with the porphyrin ligand. The cobalt salt may include one or more of a cobalt halide or cobalt ester. The cobalt salt may include cobalt halide or a cobalt acetate. The cobalt salt may include one or more of cobalt chloride or cobalt acetate.

[0011] The complex may correspond to the formula;CS is separately in each occurrence a molecule of a coordinating compound;M1 is Al:R is separately at each occurrence hydrogen, halogen, -OR2, -NRy2, -SR, -CN, -NO2, - SO2Ry, -SORy, -SO2NRy2; -CNO, -NRSO2Ry, -NCO, -N3, -SiR2; or an optionally substituted groupselected from the group consisting of C1-20 aliphatic; C1 -20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;Ry is separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl, arylalkyl; 6 to 10 membered aryl; C1-12 aliphatic; C1 -12 heteroaliphatic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two Ry on the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4 to 7 membered heterocyclic ring having 0 to 2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;R1 and R2 are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted; and,X is separately in each occurrence is a halogen or alkyl.

[0012] The complex may be formed and contacted with an epoxide and carbon monoxide under conditions to form a beta-lactone. The complex may be dissolved or suspended in the coordinating compound utilized to form the complex.

[0013] Disclosed herein are new processes to synthesize a complex (e.g., [(TPP)AI(THF)2][Co(CO)4]) useable as a carbonylation catalyst using a trisubstituted aluminum as a metalating agent and reducing agent. In the new process, trisubstituted aluminum, which is used in the metalation of the porphyrin ligand, is also used as a reducing agent of cobalt salts to form cobalt carbonyl species in situ. Cobalt carbonyl species include Co2(CO)8, Co4(CO)12, or RCo(CO)4 wherein R is a hydrocarbyl group, such as a linear or branched alkyl group having between 1 and 16 carbon atoms. By running in a mixture of coordinating compounds (e.g., THF) and inert solvents (e.g., heptane) or crystallizing the final catalyst, any residual trisubstituted aluminum or aluminum byproducts are removed by filtration. A benefit of this method is that no new metals or reagents are introduced and potentially transferred into carbonylation or polymerization that are holdovers from the catalyst synthesis reaction.Brief Description of Figures

[0014] FIG. 1 is an illustration of catalytic activity over time and conversion of EO for the catalysts formed according to Examples 1 -5.Detailed Description

[0015] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75thEd., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March’s Advanced Organic Chemistry, 5thEdition, John Wiley & Sons, Inc., New York, 2001 ; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rdEdition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.

[0016] One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed. Residue with respect to an ingredient or reactant used to prepare the polymers or structures disclosed herein means that portion of the ingredient that remains in the polymers or structures after inclusion as a result of the methods disclosed herein. Substantially or essentially all of as used herein means that greater than 90 percent of the referenced parameter, composition, structure or compound meet the defined criteria, greater than 95 percent, greater than 99 percent of the referenced parameter, composition or compound meet the defined criteria, or greater than 99.5 percent of the referenced parameter, composition or compound meet the defined criteria. Substantially or essentially free as used herein means that the reference parameter, composition, structure, or compound contains about 10 percent or less, about 5 percent or less, about 1 percent or less, about 0.5 percent or less, about 0.1 percent or less, or about 0.01 percent or less. Portion as used herein means less than the full amount or quantity of the component in the composition, stream, or both. Precipitate as used herein means a solid compound in a slurry or blend of liquid and solid compounds. The ingredients or products may exist in different states during the processes disclosed, such as solid, liquid, or gaseous state. Phase refers to a portion of a reaction mixture that is not soluble in another part of the reaction mixture. Parts per weight means parts of a component relative to the total weight of theoverall composition. Composition or mixture as used herein includes all components in a stream, reactant stream, product stream, slurry, precipitate, solution, liquid, solid, gas, or any combination thereof that are containable within a single vessel. In other words, the mixture may include components that are solid, gaseous (i.e., volatile), and / or liquid when at room temperature (i.e., 25 degrees Celsius) or when exposed to elevated temperatures. Certain polymers disclosed can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and / or diastereomers. The polymers and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers. The polymers disclosed may be enantiopure compounds. Disclosed are mixtures of enantiomers or diastereomers. In certain structures disclosed in this application parts of the structure are connected by a dotted line - which indicates that the connected structures are ionically bonded together.

[0017] The term “beta lactone”, as used herein, refers to a substituted or unsubstituted cyclic ester having a four-membered ring comprising an oxygen atom, a carbonyl group and two optionally substituted methylene groups. When unsubstituted, the beta lactone is referred to as propiolactone. Substituted beta lactones include monosubstituted, disubstituted, trisubstituted, and tetrasubstituted beta lactones. Such beta lactones may be further optionally substituted as defined herein. The beta lactones comprise a single lactone moiety. The beta lactones may comprise two or more four-membered cyclic ester moieties.

[0018] The term “epoxide”, as used herein, refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further optionally substituted as defined herein. The epoxides may comprise a single oxirane moiety. The epoxides comprise two or more oxirane moieties.

[0019] The terms “halo” and “halogen” as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).

[0020] The term “aliphatic” or “aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Aliphatic groups may contain 1-40 carbon atoms, 1-20 carbon atoms, 2-20 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, 1-6 carbon atoms, 1 -5 carbon atoms, 1 -4 carbon atoms, 1 -3 carbon atoms, or 1 or 2 carbon atoms. Aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

[0021] The term “heteroaliphatic,” as used herein, refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated, or partially unsaturated groups.

[0022] The term "unsaturated", as used herein, means that a moiety has one or more double or triple bonds. The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic”, used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring system, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined below and described herein. Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl. A cycloaliphatic group may have 3-6 carbons. The terms “cycloaliphatic”, “carbocycle” or “carbocyclic” also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring. The term “alkenyl,” as used herein, denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. The term “alkynyl,” as used herein, refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. The term “alkoxy”, as used herein refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy, include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy. The term “acyl”, as used herein, refers to a carbonyl-containing functionality, e.g., -C(=O)R’, wherein R’ is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or is a substituted (e.g., with hydrogen or aliphatic, heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogen containing functionality (e.g., forming a carboxylic acid, ester, or amide functionality). The term “acyloxy”, as used here, refers to an acyl group attached to the parent molecule through an oxygen atom. The term “aryl” used alone or as part of a larger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members. The term “aryl” may be used interchangeably with the term “aryl ring” wherein “aryl” refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents.Also included within the scope of the term “aryl”, as it is used herein, is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like, where the radical or point of attachment is on the aryl ring.

[0023] The terms “heteroaryl” and “heteroar-”, used alone or as part of a larger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 7t electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms. The term “heteroaryl” may be used interchangeably with the terms “heteroaryl ring” and “heteroaryl group”, any of which terms include rings that are optionally substituted. The term “heteroatom” refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. A heteroaryl group may be mono- or bicyclic. The term “heteroaralkyl” refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted. The term “partially unsaturated” refers to a ring moiety that includes at least one double or triple bond.

[0024] As described herein, compounds disclosed may contain “optionally substituted” moieties. The term “substituted”, whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds. The term “stable”, as used herein, refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

[0025] As used herein the term “alkoxylated” means that one or more functional groups on a molecule (usually the functional group is an alcohol, amine, or carboxylic acid, but is not strictly limited to these) has appended to it a hydroxy-terminated alkyl chain. Alkoxylated compounds may comprise a single alkyl group or they may be oligomeric moieties such as hydroxylterminated polyethers. Alkoxylated materials can be derived from the parent compounds by treatment of the functional groups with epoxides. Unless otherwise specified, “a,” “an,” “the,” and “at least one” are used interchangeably and mean one or more than one.

[0026] Epoxides of the present disclosure may be any epoxide with or without substitutions such that desirable mixtures of substituted and unsubstituted beta-lactones are formed when contacted with carbon monoxide and an appropriate catalyst system. Epoxides may be described as substituted epoxide compounds when including one or more substitutions at the carbon atom. The substituted epoxide compounds of the present disclosure may be any three membered heterocyclic compounds configured to react with carbon monoxide in the presence of an appropriate catalyst system. The epoxide may be mono or disubstituted at one or both of the carbons of the epoxide. Substitutions at the carbon atom of the epoxide may include one or more of a linear alkyl group, a branched alkyl group, an aryl group, a linear alkyl-aryl group, a branch alkyl-aryl group, a linear aryl-alkyl group, a branched aryl-alkyl group, a linear or branched alkylhalide group, or any combination thereof each of which may optionally include unsaturation. The epoxide compound may have the following structure of:

[0027] When the epoxide compound is unsubstituted, R3 each comprise hydrogen. When the epoxide is substituted, at least one of R3 independently be may be a carbon containing group which may have one or more hydrogen or fluorine atoms bonded to carbon atoms, the carbon containing groups may contain one or more of unsaturated groups, electrophilic groups, nucleophilic groups, anionic groups, cationic groups, zwitterion containing groups, hydrophobic groups, hydrophilic groups, halogen atoms, natural minerals, synthetic minerals, carbon-based particles, an ultraviolet active group, a polymer having surfactant properties, and polymerization initiators or reactive heterocyclic rings. The functional groups may be linked to the ring by a linking group (M) which functions to link the functional portion of the groups to the cyclic ring. Exemplary linking groups may be carbon containing groups, ethers, thioethers, polyethers (such as polyalkene ether). One or more of R3 may be a halogen substituted alkyl group, a sulfonic acid substituted alkyloxy group; an alkyl sulfonate alkyloxy group; alkyl ether substituted alkyl group; a polyalkylene oxide substituted alkyl group, an alkyl ester substituted alkyl group; an alkenyloxy substituted alkyl group; an aryl ester substituted alkyl group; an alkenyl group; a cyano-substitutedalkyl group; an alkenyl ester substituted alkyl group; a cycloalkyl substituted alkyl group; an aryl group; a heteroatom containing cycloalkenyl, alkyl ether substituted alkyl group; a hydroxyl substituted alkyl group, a cycloaliphatic substituted alkenyl group; an aryl substituted alkyl group; a haloaryl substituted alkyl group; an aryloxy substituted alkyl group; an alkyl ether substituted alkaryl group; a hetero atom containing cycloaliphatic group substituted alkyl group; a hetero atom containing aryl substituted alkyl group, an alkyl amide substituted alkyl group, an alkenyl substituted cycloaliphatic group; two R3 may form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted with a beta propiolactone group which may optionally be contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutenyl substituted alkyl group, optionally substituted with one or more ether groups. Beta propiolactone corresponds to the formula wherein all of the R3 are hydrogen. The R3 on one carbon atom may both be H while one or both of the selected R3 on the other carbon atom may be an optionally substituted C1-40 aliphatic, optionally substituted C1 - 20 heteroaliphatic, optionally substituted aryl or both of the selected R3 groups may be optionally taken together to form an optionally substituted ring optionally containing one or more heteroatoms. One or two of the R3 on different carbon atoms may be alkyl and the others may be hydrogen. The alkyl groups may be C1 - 20 alkyl groups, C1 -12 alkyl groups, C1 -8 alkyl groups, C1 -4 alkyl groups, wherein the alkyl groups may contain unsaturation, heteroatoms or heteroatom containing functional groups. One or two of the R3 on different carbon atoms may be methyl or ethyl and the others may be hydrogen. Two of R3 on the same carbon atom may be methyl while the other of the selected R3 are hydrogen. When the epoxide compound is mono or di substituted at a single carbon and configured to ring open and form either or both of a beta or alpha substituted beta lactone, only one carbon include at least one substitution at R3 that comprises one or more of the other groups described herein.

[0028] The lactone or beta propiolactone formed from a carbonylation reaction may be any cyclic carboxylic ester having at least one carbon atom and two oxygen atoms. For example, the lactone may be an acetolactone, a beta propiolactone, a butyrolactone, a valerolactone, caprolactone, or a combination thereof. Anywhere in this application where a propiolactone or lactone is used or described, another lactone may be applicable or usable in the process, step, or method. Where a propiolactone is a used or produced in the carbonylation reaction, the propiolactone may have a structure corresponding to:

[0029] The beta-lactones correspond to the general formula:wherein R3is defined herein.

[0030] By the new method described here, pre-formed or isolated Co2(CO)8 is not utilized, and the cobalt carbonyl species is formed in situ by a relatively low pressure and low temperature route. Simple cobalt salts can be used as the cobalt source and an alkylaluminum compound is used as the reducing agent. Depending on the starting materials, a range of pressures (10-450 psi) and temperatures (30-120 oC) have been used to form carbonylation catalyst and are significantly lower than those used in Co2(CO)8 synthesis.

[0031] The cobalt carbonyl can be formed in the presence of (TPP)AICI to form the catalyst in situ. This process could be performed in two ways. In the first, a cobalt salt is reacted with a trialkylaluminum reagent and pressurized with CO to form cobalt carbonyl(s). A pre-formed tetraphenyl porphyrin aluminum chloride or tetraphenyl porphyrin aluminum alkyl complex added to the reaction mixture will react with the cobalt carbonyl to form the carbonylation catalyst. In the alternative route, tetraphenylporphyrin is reacted with 2 mol equivalents excess alkylaluminum reagent in a nonpolar solvent to form the tetraphenyl porphyrin aluminum chloride or tetraphenyl porphyrin aluminum alkyl complex. A cobalt salt and THF are added to the reaction mixture which is then pressurized with CO. The residual alkylaluminum from the first step acts as the reducing agent, forming cobalt carbonyl(s). The cobalt carbonyl(s) subsequently react with the tetraphenyl porphyrin aluminum chloride or tetraphenyl porphyrin aluminum alkyl complex to form carbonylation catalyst.

[0032] Both tetraphenylporphyrin aluminum chloride and tetraphenylporphyrin aluminum alkyl have been converted to carbonylation catalyst by the new method. Reduction of several cobalt salts, including CoCI2, Co(OAc)2, CoBr2, Co(stearate)2, Co(2-ethylhexanoate)2, and Co(acac)2, to cobalt carbonyls are shown. AIEt3, AI(iBu)3, Et2AICI, and Al(octyl)3 have been used as reducing agents to form carbonylation catalyst.

[0033] Depending on the Co salt and alkylaluminum used, up to three different cobalt carbonyl species were observed by FTIR in varying ratios: Co2(CO)8, Co4(CO)12, and RCoCo(CO)4 (where R is a hydrocarbyl group). All three can presumably react with (TPP)AIEt to form carbonylation catalyst. However, the conditions that formed a higher ratio of Co2(CO)8 also led to higher conversion to carbonylation catalyst.

[0034] In one aspect, the method may include contacting a cobalt salt comprising one or more of a cobalt halide and / or ester with a trialkylaluminum or halodialkylaluminum in a coordinating compound and / or an inert solvent to form a solution. The method may include contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of from about 25 °C to about 100 °C under conditions to form cobalt carbonyl. The method may include contacting the cobalt carbonyl with a porphyrin metal halide or alkyl and a coordinating compound, and optionally an inert solvent, under conditions to form a complex of a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.

[0035] The step of contacting the cobalt salt and the trialkylaluminum or halodialkylaluminum in the coordinating compound and / or inert solvent to form a solution may be conducted first. The step may be conducted before, after, or during the application of pressure and / or temperature. The step of contacting the cobalt salt and the trialkylaluminum or halodialkylaluminum may be conducted in a water or oxygen free environment or may be conducted at the ambient conditions. The step of contacting the cobalt salt and the trialkylaluminum or halodialkylaluminum may be conducted before application of or under pressure that includes carbon monoxide gases. The application of carbon monoxide gases under pressure may induce formation of the cobalt carbonyl. Optionally, other gases that are inert may be present such as nitrogen, argon, helium, neon, krypton, xenon, radon, or any combination thereof. The step of contacting the cobalt salt and trialkylaluminum or halodialkylaluminum may be conducted at any pressure sufficient to form the cobalt carbonyl or the carbonylation catalyst (where the porphyrin metal halide is present). The pressure may be about 50 kPa or more, about 400 kPa or more, or about 1000 kPa or more. The pressure may be about 4000 kPa or less, about 3000 kPa or less, or about 2000 kPa or less. The reaction steps described herein may be conducted in a pressurized reactor, a Schlenk line, a glove box, or any combination thereof.

[0036] The step of contacting the cobalt salt and the trialkylaluminum or halodialkylaluminum may be mixed with or without agitation for a period of time sufficient to dissolve one or more components in the coordinating compound and / or inert solvent to form the solution. For example, the time may be about 30 seconds or more, about 5 minutes or more, or about 15 minutes or more. The time may be about 30 minutes or less, about 25 minutes or less, or about 20 minutes or less. The time of mixing the cobalt salt and the trialkylaluminum or halodialkylaluminum before application of the carbon monoxide may be negligible or simultaneous. The step of contacting the cobalt salt and the trialkylaluminum or halodialkylaluminum may be conducted before or simultaneously to the application of carbon monoxide under pressure. The step of contacting thecobalt salt and the trialkylaluminum or halodialkylaluminum may be conducted and one or more separation techniques described herein may be applied to the solution before application of the carbon monoxide under pressure.

[0037] The solution may be formed or have carbon monoxide pressure applied to it at a temperature sufficient to form the cobalt carbonyl in the solution. The cobalt salt and the trialkylaluminum or halodialkylaluminum may be contacted at a temperature sufficient to form the solution. The carbon monoxide may be contacted with the solution under a temperature sufficient to form the cobalt carbonyl without negatively impacting the trialkylaluminum or halodialkylaluminum. The temperature pressure may be sufficient to retain the coordinating compound in a liquid state. The cobalt salt and the trialkylaluminum or halodialkylaluminum may be contacted at a first temperature that is different than a second temperature in which the carbon monoxide is contacted with the solution. The second temperature may be less or more than the first temperature. The cobalt salt, trialkylaluminum or halodialkylaluminum, and / or the carbon monoxide may all be contacted at the same temperature. The temperature (or first or second temperature) may be about 25 degrees Celsius or more, about 50 degrees Celsius or more, or about 75 degrees Celsius or more. The temperature may be about 110 degrees Celsius or less, about 100 degrees Celsius or less, or about 90 degrees Celsius or less. During or after application of pressure of the carbon monoxide, the solution may be mixed for any period of time sufficient to form the cobalt carbonyl. The period of time may be about 5 minutes or more, about 10 minutes or more, or about 30 minutes or more. The period of time may be about 3 hours or less, about 2 hours or less, or about 1 hour or less. After forming the cobalt carbonyl in the solution, the solution may be subjected to one or more separation steps as described herein. The separation steps may be configured to remove one or more unreacted starting components (i.e., trialkylaluminum, halodialkylaluminum, and / or cobalt salt), byproduct from the formation of the cobalt carbonyl, and / or the coordinating compound and / or inert solvent such that the cobalt carbonyl is in a state sufficient to be contacted with the porphyrin metal halide or alkyl under conditions sufficient to form complex configured as a carbonylation catalyst.

[0038] Once the cobalt carbonyl is formed, the solution may be contacted with a porphyrin metal halide or alkyl and optionally another or more of the same coordinating compound and / or an inert solvent under such conditions as to form a complex configured as a carbonylation catalyst. The porphyrin metal halide or alkyl may be added under ambient conditions or in an oxygen and / or water free environment. The porphyrin metal halide or alkyl and the solution may be contacted for a period of time, optionally under elevated pressure (e.g., using inert gases as described herein) and / or temperature, sufficient to form the complex without damaging the porphyrin ligands and / orcobalt carbonyls. The period of time may be about 10 minutes or more, about 30 minutes or more, or about 1 hour or more. The period of time may be about 4 hours or less, about 3 hours or less, or about 2 hours or less. The temperature may be the same or different than the temperature of the solution during contacting of the carbon monoxide. The temperature may be about 25 degrees Celsius or more, about 50 degrees Celsius or more, or about 75 degrees Celsius or more. The temperature may be about 110 degrees Celsius or less, about 100 degrees Celsius or less, or about 90 degrees Celsius or less. The pressure may be about 50 kPa or more, about 400 kPa or more, or about 1000 kPa or more. The pressure may be about 4000 kPa or less, about 3000 kPa or less, or about 2000 kPa or less.

[0039] In one aspect, the method may include contacting a trialkylaluminum or halodialkylaluminum with a porphyrin ligand and in inert solvent to form a solution containing a porphyrin metal halide or alkyl. The method may include contacting the solution of with a cobalt salt comprising one or more of a cobalt halide and / or ester to make a formed solution. The method may include contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of about 10 °C to about 120 °C in the presence of a coordinating compound under conditions to form a complex containing a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.

[0040] The step of contacting the porphyrin ligand and the trialkylaluminum or halodialkylaluminum in the inert solvent to form a solution may be conducted before or simultaneous with the addition of the cobalt salt. The step may be conducted before, after, or during the application of pressure and / or temperature and / or the cobalt salt. The step of contacting the porphyrin ligand, cobalt salt, and / or the trialkylaluminum or halodialkylaluminum may be conducted in a water or oxygen free environment or may be conducted at the ambient conditions. The step of contacting the porphyrin ligand, cobalt salt, and / or the trialkylaluminum or halodialkylaluminum may be conducted before application of or under pressure that includes carbon monoxide gases. The application of carbon monoxide gases under pressure may induce formation of the cobalt carbonyl. Optionally, other gases that are inert may be present such as nitrogen, argon, helium, neon, krypton, xenon, radon, or any combination thereof. The step of contacting the porphyrin ligand, cobalt salt, and / or the trialkylaluminum or halodialkylaluminum may be conducted at any pressure sufficient to form the cobalt carbonyl or the carbonylation catalyst (where the porphyrin metal halide is present). The pressure may be about 50 kPa or more, about 400 kPa or more, or about 1000 kPa or more. The pressure may be about 4000 kPa or less, about 3000 kPa or less, or about 2000 kPa or less. The reaction steps described hereinmay be conducted in a pressurized reactor, a Schlenk line, a glove box, or any combination thereof.

[0041] The step of contacting the porphyrin ligand, cobalt salt, and / or the trialkylaluminum or halodialkylaluminum may be mixed with or without agitation for a period of time sufficient to dissolve one or more components in the coordinating compound and / or inert solvent to form the solution. For example, the time may be about 30 seconds or more, about 5 minutes or more, or about 15 minutes or more. The time may be about 30 minutes or less, about 25 minutes or less, or about 20 minutes or less. The time of mixing the porphyrin ligand and the trialkylaluminum or halodialkylaluminum before application of the carbon monoxide may be negligible or simultaneous with addition of the cobalt salt. The step of contacting the porphyrin ligand and the trialkylaluminum or halodialkylaluminum may be conducted before or simultaneously to the application of carbon monoxide under pressure and / or addition of the cobalt salt. The step of contacting the porphyrin ligand and the trialkylaluminum or halodialkylaluminum may be conducted and one or more separation techniques described herein may be applied to the solution before application of the carbon monoxide under pressure and / or addition of the cobalt salt.

[0042] The solution may be formed or have carbon monoxide pressure applied to it at a temperature sufficient to form the complex when the cobalt salt is present. At any time before, during, or after addition of the cobalt salt to the solution, the coordinating compound may be added to the solution. It is believed without being bound by any theory that a cobalt carbonyl intermediate and / or porphyrin metal halide or alkyl may be formed when the cobalt salt, trialkylaluminum or halodialkylaluminum, and porphyrin ligand are mixed. The complex may additionally be formed when the coordinating compound is added and subsequently coordinates to the aluminum or other metal of the porphyrin metal halide. The porphyrin ligand, the cobalt salt and the trialkylaluminum or halodialkylaluminum may be contacted in the inert solvent and / or coordinating compound at a temperature sufficient to form the solution. The carbon monoxide may be contacted with the solution under a temperature sufficient to form the cobalt carbonyl without negatively impacting the trialkylaluminum or halodialkylaluminum or porphyrin metal halide or alkyl. The temperature pressure may be sufficient to retain the coordinating compound in a liquid state. The porphyrin ligand, and the trialkylaluminum or halodialkylaluminum may be contacted at a first temperature that is different than a second temperature in which the carbon monoxide and / or cobalt salt is contacted with the solution. The second temperature may be less or more than the first temperature. The cobalt salt, porphyrin ligand, trialkylaluminum or halodialkylaluminum, and / or the carbon monoxide may all be contacted at the same temperature.The temperature (or first or second temperature) may be about 25 degrees Celsius or more, about 50 degrees Celsius or more, or about 75 degrees Celsius or more. The temperature may be about 1 10 degrees Celsius or less, about 100 degrees Celsius or less, or about 90 degrees Celsius or less. During or after application of pressure of the carbon monoxide, the solution may be mixed for any period of time sufficient to form the cobalt carbonyl. The period of time may be about 5 minutes or more, about 10 minutes or more, or about 30 minutes or more. The period of time may be about 3 hours or less, about 2 hours or less, or about 1 hour or less. After forming the cobalt carbonyl, porphyrin metal halide or alkyl, or the complex in the solution, the solution may be subjected to one or more separation steps as described herein. The separation steps may be configured to remove one or more unreacted starting components (i.e., trialkylaluminum, halodialkylaluminum, and / or cobalt salt), byproduct from the formation of the cobalt carbonyl or the porphyrin metal halide or alkyl, and / or the coordinating compound and / or inert solvent such that the cobalt carbonyl is in a state sufficient to be contacted with the porphyrin metal halide or alkyl under conditions sufficient to form complex configured as a carbonylation catalyst.

[0043] In all of or at each individual step of contacting the carbon monoxide, the porphyrin ligand, cobalt salt, trialkylaluminum or halodialkylaluminum, coordinating compound and / or an inert solvent, and / or porphyrin metal halide or alkyl, the components may be agitated by any means and for any period of time in a reaction vessel sufficient to form the complex useable as a carbonylation catalyst. The reaction vessel(s) may contain one or more reaction zones, and may include, a batch reactor, a continuous stirred-tank reactor, a plug flow reactor, semi-batch reactor, a catalytic reactor, a continuous flow reactor, or any combination thereof. The vessel may be equipped with a mechanism for mixing the reaction, such as an agitator, impeller, or a combination of both. In other examples, the reaction may be mixed by the flow of fluids within a reactor, such as sparging or turbulent flow. The residence time of the reaction may be about 1 minute or more, about 5 minutes or more, or about 30 minutes or more. The residence time may be 240 minutes or less, about 200 minutes or less, or about 100 minutes or less.

[0044] The cobalt salt and the trialkylaluminum or halodialkylaluminum may be contacted in any molar ratio sufficient to form the cobalt carbonyl. The cobalt salt and the trialkylaluminum or halodialkylaluminum may be contacted in any molar ratio sufficient to form the complex with limited byproducts. The cobalt salt and the trialkylaluminum or halodialkylaluminum may be contacted in a molar ratio of about 4:1 or more, about 3:1 or more, or about 2:1 or more. The cobalt salt and the trialkylaluminum or halodialkylaluminum may be contacted in a molar ratio of about 1 :4 or less, about 1 :3 or less, or about 1 :2 or less. The porphyrin ligand and the trialkylaluminum or halodialkylaluminum may be contacted in any molar ratio sufficient to form theporphyrin metal halide and / or alkyl. The porphyrin ligand and the trialkylaluminum or halodialkylaluminum may be contacted in any molar ratio sufficient to form the porphyrin metal halide an / dor alkyl with limited byproducts. The porphyrin ligand and the trialkylaluminum or halodialkylaluminum may be contacted in a molar ratio of about 4:1 or more, about 3:1 or more, or about 2:1 or more. The porphyrin ligand and the trialkylaluminum or halodialkylaluminum may be contacted in a molar ratio of about 1 :4 or less, about 1 :3 or less, or about 1 :2 or less. The cobalt salt and / or porphyrin metal halide or alkyl may be present in the solution in any ratio sufficient to form the complete (i.e., carbonylation catalyst). The molar ratio of may be about 4:1 or more, about 3:1 or more, or about 2:1 or more. The molar ratio of (cobalt salt and / or cobalt tetracarbonyl salt) / porphyrin metal halide or alkyl may be about 1 :4 or less, about 1 :3 or less, or about 1 :2 or less.

[0045] The cobalt salt may be configured to form a cobalt carbonyl when contacted with the trialkylaluminum or halodialkylaluminum and carbon monoxide under appropriate pressure and / or temperature conditions. The cobalt salt may comprise cobalt and an appropriate counterion. The counterion may be an appropriate anion. The counterion alone or in combination with other counterions may have any charge sufficient to balance the charge of the cobalt. Each of the counterions may have a negative charge of 1 , 2, or 3. The cobalt may have positive charge of 2. The counterion may include one or more halides, esters, or any combination thereof. The halides may include one or more chloride, fluorine, bromine, and / or iodine. The ester may include one or more ester groups having an anionic end at an oxygen atom and a substituted end attached to a carbon atom of a carbonyl. The substituted end may include one or more of a linear or branched alkyl group, alkyl-aryl group, an aryl-alkyl group, aryl group, cycloalkyl, or any combination thereof including between C1 -24 optionally including unsaturation along the chain of carbons. The ester may include one or more of a stearate, acetate, 3-ethylhexanoate, or any combination thereof. The cobalt salt may have a configuration of CoX2 where X comprises a halide, an acetate, an ester, or any combination thereof. The cobalt salt may be CoCI2, Co(OAc)2, CoBr2, Co(stearate)2, Co(2-ethylhexanoate)2, and Co(acac)2, or any combination thereof.

[0046] The trialkylaluminum or halodialkylaluminum may have one or more functionalities in the solution. The trialkylaluminum or halodialkylaluminum may be configured to reduce the cobalt salt such that a cobalt carbonyl forms under appropriate carbon monoxide pressure and temperature application. The trialkylaluminum or halodialkylaluminum may be configured to form a porphyrin metal halide and / or alkyl when contacted with a porphyrin ligand. The trialkylaluminum or halodialkylaluminum may be soluble or insoluble in the coordinate compound and / or inert solvent. The trialkylaluminum or halodialkylaluminum may be any aluminum centered compound havingat least 3 substitutions. The alkyl substitution may be any alkyl group described herein such as one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or other appropriate alkyl groups having between 1 and 20 carbons. The halo substitution may be any appropriate halogen, such as chloride, bromide, iodide, or the like. The halodialkylaluminum and trialkylaluminum may have a structure of AIR3, where Al is aluminum, at least two Rs are an alkyl substitution, and optionally one R is a halogen. The halodialkylaluminum and trialkylaluminum may be used independently of each or together in an appropriate molar ratio. The molar ratio of halodialkylaluminum / trialkylaluminum may be about 4:1 or less about 2:1 or less, or about 1 :1 or less. The molar ratio may be about 1 :4 or more, about 1 :2 or more, or about 1 :1 or more. In some examples, a dihaloalkylalumnium compound may be used in place of the trialkylaluminum or halodialkylaluminum.

[0047] The cobalt carbonyl may function as an intermediate between the cobalt salt and the complex that is configured to be used as a carbonylation catalyst. The cobalt carbonyl may comprise residues of the cobalt salt and the carbon monoxide. To form the cobalt carbonyl with the cobalt salt and trialkylaluminum or halodialkylaluminum, the carbon monoxide may be present in excess relative to the molar amount of cobalt salt at the pressures described herein. For example, the pressure may be about 50 kPa or more, about 400 kPa or more, or about 1000 kPa or more. The pressure may be about 4000 kPa or less, about 3000 kPa or less, or about 2000 kPa or less. The cobalt carbonyl may a number of cobalt atoms coordinated to carbonyls. The combination of cobalt atoms coordinated to carbonyls may further be associated with other combinations of cobalt tarns coordinated to carbonyls. The cobalt carbonyl may include two or four carbonyls per cobalt atom. The cobalt carbonyl may include any number of cobalt atoms in appropriately balanced pairs, such as two or more, four or more, eight or more, or sixteen or more. Cobalt carbonyl species include Co2(CO)8, Co4(CO)12, or RCo(CO)4 wherein R is a hydrocarbyl group, such as a linear or branched alkyl group having between 1 and 16 carbon atoms The cobalt carbonyl may have a formula that corresponds to the formula (Cox(CO)y; wherein, x is an integer of from 1 to 8; and y an integer of from 1 to 32.

[0048] The porphyrin ligand may function as a precursor to the porphyrin metal halide or alkyl. The porphyrin ligand may be any heterocyclic macrocycle organic compound that is configured to form the porphyrin metal halide or alkyl. The porphyrin ligand may be an unsubstituted or substituted porphin. The porphyrin ligand may include a tetraphenyl porphyrin compound that optionally includes additional substitution on the phenyl groups or along other portions of the porphyrin. The porphyrin ligand may be free of metals. The porphyrin ligand may be free of heteroatoms other than nitrogen.

[0049] The porphyrin metal halide or alkyl may function as precursor ligand to the complex that is used as a carbonylation catalyst. The porphyrin metal halide or alkyl may include a porphyrin ligand that is coordinated to a metal center and a halide coordinated to the metal center. The metal center may be any metal configured to form a cation when coordinated to the coordinating compound and the ligand. The metal center may include one or more of aluminum, chromium, iron, cobalt , titanium, gallium, manganese, indium, or any combination thereof. The porphyrin metal halide or alkyl may be soluble or insoluble in one or more of the coordinating compounds and / or inert solvents. Once the coordinating compound is coordinated to the metal center of the porphyrin and the halide or alkyl is displaced, the complex may be formed. The porphyrin metal halide or alkyl may include one or more substitutions along the porphyrin complex. The substitutions may include one or more hydrogen, phenyl groups, alkyl groups, alkyl-aryl groups, aryl alkyl groups, chlorine groups, alkoxy group, fluorine groups, or any combination thereof. The substitutions may be positioned at symmetrical locations along porphyrin ring.

[0050] The porphyrin metal halide or alkyl may have the following structure:M1is separately in each occurrence a metal:R is separately at each occurrence hydrogen, halogen, -OR2, -NRy2, -SR, -CN, -NO2, - SO2Ry, - SORy, -SO2NRy2; -CNO, -NRSO2Ry, -NCO, -N3, -SiR2; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatomsindependently selected from the group consisting of nitrogen, oxygen, and sulfur; Ryis separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl, arylalkyl; 6 to 10 membered aryl; C1-12 aliphatic; C1-12 heteroaliphatic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two Ryon the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4 to 7 membered heterocyclic ring having 0 to 2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;R1and R2are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted; and,Xi is separately in each occurrence is a halogen or alkyl group.

[0051] The complex comprising a cation of a porphyrin metal wherein the coordinating compound is coordinated to the metal and an anion comprising a cobalt tetracarbonyl. As used herein, complex may be interchangeable with carbonylation catalyst. The carbonylation catalyst may be a combination of an anionic compound and a cationic compound. The porphyrin metal halide once integrated into the complex may be described as a metalated ligand complex that is free of halides. The carbonylation catalyst may include one or more other coordinating compounds coordinated to the metal of the metalated ligand compound so that the coordinating compounds used herein may have a dual purpose (i.e., facilitating the reaction and coordinating to the metal). The carbonylation catalyst may include at least two metal compounds that are ionically affiliated with each other. For example, an aluminum integrated with a ligand complex may be ionically affiliated with a cobalt carbonyl. The carbonylation catalyst may include any metal that is contained within the metalated ligand complex, the metal carbonyl, or both. The carbonylation catalyst may be any catalyst containing a metal center and having catalytic activity with one or more of an epoxide, succinic anhydride, a lactone, an aziridine, a lactam or any combination thereof. The metal of the cationic or anionic component of the carbonylation catalyst may be any metal sufficient to catalyze a carbonylation or ring opening reaction. The carbonylation catalyst may have one or more structures shown in US Provisional Application Nos. 63 / 171 ,150 (filed on April 6, 2021 ); 63 / 220,126 (filed on July 9, 2021 ); and / or 63 / 171 ,152 (filed on April 6, 2021 ), USPublication No. 2017 / 0225157 (filed on July 24, 2017), and / or US Patent Nos. 9,327,280 and 8,921 ,581 , which are each incorporated herein by reference in their entirety.

[0052] The complex useable as a carbonylation complex may have the following structure:wherein:CS is separately in each occurrence a molecule of a coordinating solvent;M1is separately in each occurrence a metal; andR is separately at each occurrence hydrogen, halogen, -OR2, -NRy2, -SR, -CN, -NO2, - SO2Ry, - SORy, -SO2NRy2; -CNO, -NRSO2Ry, -NCO, -N3, -Si R2; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; Ryis separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl, arylalkyl; 6 to 10 membered aryl; C1-12 aliphatic; C1-12 heteroaliphatic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the groupconsisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two Ryon the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4 to 7 membered heterocyclic ring having 0 to 2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;R1and R2are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted.

[0053] Before using the complex as a carbonylation catalyst, the complex may be removed from the reaction mixture or solution by any separation means sufficient to yield a complex with catalytic activity to form a lactone. The complex may be insoluble or soluble in one or more of the inert solvent and / or coordinating compound. Any technique known by the skilled artisan may be used as a separation means to separate solids and liquids and yield the complex as a solid in a form that has catalytic activity and yield the other components as a liquid or solid separate from the complex. For example, the single vessel used in the first and second steps may be subjected to a filtering means that collects the complex in a form of a precipitate, and a container of any form may be positioned under the separation means to collect the components of the reaction mixture having a form that is liquid. The third step may be performed under conditions that are free of air, moisture, and / or oxygen so that the stability of the complex is not affected and undesirable side reactions do not occur. The separation means may utilize any technique or device sufficient to collect a precipitate and allow a liquid to drain through the filter. For example, the separation means may include one or more of a vacuum filters, gravity filters, centrifugation means, decantation means, surface filters, depth filters, hot filtration, cold filtration, or any combination thereof. The third step may include pouring or contacting additional coordinating compounds and / or inert solvents over the precipitate containing the complex to rinse the precipitate of additional undesirable impurities that are contained within the precipitate and are soluble in the coordinating compounds and / or inert solvents, which may be referred to as a rinsing step within the third step. The rinsing step may include adding or contacting of any amount of coordinating compounds and / or inert solvents sufficient to wash away any undesirable impurities contained within the precipitate and subjecting the precipitate that contains complex to a separation means. The third step may additionally include a separation step to separate any remaining coordinating compounds and / or inert solvents from the precipitate. The separation step may include any technique sufficient to separate the coordinating compounds and / or inert solvents from the precipitate, such as subjecting the precipitate to one or more of the separation means described herein. For example, the separation step may include applying a vacuum to the precipitate toremove the coordinating compounds and / or inert solvents from the precipitate to yield the catalyst. The separation step may include applying heat to the precipitate to remove the coordinating compounds and / or inert solvents from the precipitate to yield the catalyst. Any amount of heat may be applied so long as the heat is not so high that the heat affects the stability of the carbonylation catalyst. For example, the heat may be applied to raise the temperature of separation step to about 110 degrees Celsius or less, about 90 degrees Celsius or less, or about 70 degrees Celsius or less. The heat may be applied to raise the temperature of separation step to may be about 40 degrees Celsius or more, about 50 degrees Celsius or more, or about 60 degrees Celsius or more. The separation step may include applying a nitrogen stream to the precipitate to remove the coordinating compounds and / or inert solvents from the precipitate.

[0054] The present disclosure discusses certain compositions and methods that use the described complexes. The present complexes described may further be used in formation of lactones (e.g., beta propiolactone). The complexes may be contacted with an epoxide compound and carbon monoxide, optionally in the presence of a solvent, under such conditions such that a lactone is formed. Methods for forming lactones using complexes (i.e., carbonylation catalysts that include porphyrin ligands) may be described in WO2024049975, WO2022221086A1 , US10927091 B2, which are incorporated herein by reference in their entirety. The compositions described herein may include components of a carbonylation reaction at the start, in the middle of, or at completion of the reaction. The compositions of the current disclosure may include minimal starting components (cobalt salt, trialkyl or halodialkyl alumnium, porphyrin ligand, and / or porphyrin metal halide or alkyl) and / or byproduct after or without separation steps applied to the complex. The starting components and / or byproducts may be present in an amount of about 100,000 p / g or less, about 50,000 p / g or less, or about 25,000 p / g or less. The starting components and / or I byproduct may be present in an amount of about 1 ,000 p / g or more, about 5,000 p / g or more, or about 10,000 p / g or more.

[0055] The coordinating compound functions to coordinate to the complex such that the complex is useable as a carbonylation catalyst. The coordinate compound additionally may function to dissolve one or more compounds in the disclosed methods, such as the cobalt salts, cobalt tetracarbonyl salts, the porphyrin metal halide, and / or the complex (i.e., carbonylation catalyst). The coordinating compound may include at least one heteroatom. The coordinating compound may be a polar aprotic solvent. The coordinating compound may be a compound with at least two free valence electrons. For example, the coordinating compound may include one or more ester solvents, ketone solvents, aldehyde solvents, ether solvents, or any combination thereof. The coordinating compound may be configured to dissolve one or more compounds with polar portionsand / or coordinate to a porphyrin metal halide or a carbonylation catalyst. The coordinating compound may include sulfur, nitrogen, oxygen, carbon, hydrogen, a halogen, or any combination thereof. The coordinating compound may include heterocyclic compounds containing nitrogen, ethers, nitriles, esters, ketones, acetates, or any combination thereof. The coordinating compound may be tetrahydrofuran, 2,5-dimethyl tetrahydrofuran, sulfolane, N-methyl pyrrolidone, 1 ,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ethers, methyl tertbutyl ether, diethylether, diphenyl ether, 1 ,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, dibasic esters, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxy ethane, acetone, methylethyl ketone, or mixture thereof. The coordinating compound may be a nonpolar solvent. The inert solvent may be contacted with the porphyrin metal halide, the cobalt salt, the trialkyl or halodialkyl aluminum, or inert solvent in excess.

[0056] The inert solvent may function to dissolve one or more of the cobalt salts, cobalt carbonoyl, the porphyrin metal halide, and / or the complex (i.e., carbonylation catalyst). The inert solvent may either not coordinate to porphyrin metal halide or a carbonylation catalyst or the inert solvent may have a lesser affinity to the metal of the porphyrin metal halide or a carbonylation catalyst compared to the coordinating compound. The inert solvent may be different than the coordinating compound. The inert solvent may have a polarity sufficient to phase separate from the complex or one or more of the starting components. The inert solvent may be a nonpolar solvent. The inert solvent may be contacted with the porphyrin metal halide, the cobalt salt, the trialkyl or halodialkyl aluminum, or coordinating compound in excess. The inert solvent may be present relative to the coordinating compound in a volumetric ratio sufficient to allow formation of the cobalt carbonyl, porphyrin metal halide or alkyl, and / or complex in the solution. The volumetric ratio may be about 1 :1 or more, about 2:1 or more, or about 4:1 or more. The volumetric ratio may be about 1 :4 or less, about 1 :2 or less, or about 1 :1 or less. The inert solvent may be an alkyl and / or aromatic solvent. The inert solvent may be an alkane. The inert solvent may be a non-polar cyclic ether. The inert solvent may be a solvent that is free of oxygen or nitrogen atoms. The inert solvent may include one or more of pentane, hexane, benzene, heptane, and / or toluene.

[0057] Reaction Scheme 1 and 2 (respectively shown) below illustrate techniques to make complexes as described herein.

[0058] Reaction scheme 1 illustrates addition of a cobalt salt (Co2X; 1 equivalent) in a solution to 1 ) trialkyl aluminum (AEt3; 2 equivalents) in a coordinating compound (THF) an optionally an inert solvent (“other solvent) for a short period of time (i.e., less than 10 mins); and 2) applyingcarbon monoxide (CO) at 450 psi at100 degrees Celsius for about 2 hours. Steps 1) and 2) may be conducted in sequence or in sequence. The combination of steps 1 ) and 2) forms a cobalt carbonyl ([Co2(CO)8]). After formation of the cobalt carbonyl, either a porphyrin metal halide or alkyl ((TPP)AICI or (TPP)AIEt) is added to the solution form the complex, which comprises the porphyrin metal coordinated with the coordinating compound in cationic form and a cobalt carbonyl in anionic form.

[0059] Reaction scheme 2 illustrates addition of a porphyrin ligand (1 equivalent) in a solution to 1 ) trialkyl aluminum (AIEt3; 3 equivalents) in a inert solvent (heptane); and 2) a cobalt salt (Co(OAc)2; 1 equivalent) and carbon monoxide (CO) stream at 450 psi at100 degrees in a coordinating compound (THF). Steps 1 ) and 2) may be conducted in sequence or in sequence. The combination of steps 1 ) and 2) forms the complex, which comprises the porphyrin metal coordinated with the coordinating compound in cationic form and a cobalt carbonyl in anionic form.ENUMERATED EMBODIMENTS1 . A method comprising: a) contacting a cobalt salt comprising one or more of a cobalt halide or ester with a trialkylaluminum or halodialkylaluminum in a coordinating compound and / or an inert solvent to form a solution;b) contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of from about 25 °C to about 100 °C under conditions to form cobalt carbonyl: and c) contacting the cobalt carbonyl with a porphyrin metal halide or alkyl and a coordinating compound, and optionally an inert solvent, under conditions to form a complex of a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.2. The method of Embodiment 1 wherein molar ratio of the trialkylaluminum or halodialkylaluminum to the cobalt salt is 2.0 to 1 .0 or greater.3. The method of Embodiment 1 or 2 wherein the inert solvent is a non-polar ether, aromatic solvent, or alkane.4. The method of any one of Embodiments 1 to 3 wherein the coordinating compound and / or an inert solvent is diethyl ether, tetrahydrofuran, toluene, or heptane.5. The method of any one of Embodiments 1 to 4 wherein the porphyrin metal halide or alkyl and cobalt carbonyl are contacted such that there is a molar excess of porphyrin metal halide or alkyl.6. The method of any one of Embodiments 1 to 5 wherein the porphyrin metal halide or alkyl and cobalt carbonyl are contacted at a molar ratio of 2.0. : 1 or greater.7. The method of any one of Embodiments 1 to 6 wherein an molar ratio or greater of the coordinating compound is contacted with porphyrin metal halide or alkyl.8. A method comprising contacting: a) contacting a trialkylaluminum or halodialkylaluminum with a porphyrin ligand and in inert solvent to form a solution containing a porphyrin metal halide or alkyl; b) contacting the solution of with a cobalt salt comprising one or more of a cobalt halide or ester to make a formed solution; and, c) contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of about 10 °C to about 120 °C in the presence of a coordinating compound under conditions to form a complex containing a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.9. The method of Embodiment 8 wherein the molar ratio of the trialkylaluminum or halodialkylaluminum to cobalt salt is 3.0:1 .0 or greater.10. The method of any one of Embodiment 8 or 9 wherein the inert solvent is an alkane or aromatic solvent.11. Themethod of any one of Embodiments 8 to 10 the inert solvent is toluene, heptane, or a hexane.12. The method of any one of Embodiments 8 to 1 1 wherein an equivalent excess of the trialkylaluminum or halodialkylaluminum is contacted with the tetraphenylporphyrin.13. The method of any one of Embodiments 8 to 12 wherein the trialkylaluminum or halodialkylaluminum is contacted with the tetraphenylporphyrin at a molar ratio of about 3.0:1.0 or greater.14. The method of any one of Embodiments 8 to 13 wherein an equivalent excess of the coordinating compound is contacted with the porphyrin ligand.15. The method of any of the preceding embodiments wherein the cobalt salt comprises one or more of a cobalt halide or cobalt ester.16. The method of any of the preceding embodiments wherein the cobalt salt comprises a cobalt halide or a cobalt acetate17. The method of any of the preceding embodiments wherein the cobalt salt comprises one or more of cobalt chloride or cobalt acetate.18. The method of any of the preceding embodiments wherein the porphyrin metal halide or alkyl compound corresponds to the formula;wherein:CS is separately in each occurrence a molecule of a coordinating compound;M1 is Al:R is separately at each occurrence hydrogen, halogen, -OR2, -NRy2, -SR, -CN, -NO2, - SO2Ry, -SORy, -SO2NRy2; -CNO, -NRSO2Ry, -NCO, -N3, -SIR2; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1 -20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;Ry is separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl, arylalkyl; 6 to 10 membered aryl; C1-12 aliphatic; C1 -12 heteroaliphatic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two Ry on the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4 to 7 membered heterocyclic ring having 0 to 2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;R1 and R2 are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted; and,X is separately in each occurrence is a halogen or alkyl.19. The method of Embodiment 18 wherein:CS is separately in each occurrence a molecule of a dihydrocarbyl ether, alkylene ether or cyclic ether.R is separately at each occurrence hydrogen or alkyl,R1 and R2 are separately in each occurrence phenyl or substituted alkyl; and,X is separately in each occurrence is alkl, chlorine or bromine.20. The method of Embodiment 19 wherein:CS is separately in each occurrence a molecule of a cyclic ether;R is separately at each occurrence hydrogen.R1 is separately in each occurrence an optionally substituted phenyl group or an optionally substituted alkyl group; and,X is separately in each occurrence is ethyl, chlorine or bromine.21 . The method of any one of the preceding embodiments wherein the coordinating compound is a dihydrocarbyl ether, a polyalkylene oxide or a cyclic ether.22. The method of any one of the preceding embodiments wherein the coordinating compound is a cyclic ether.23. The method of any one of the preceding embodiments wherein the coordinating compound is dioxane or tetrahydrofuran.24. The method of any one of the preceding embodiments wherein the complex formed is contacted with an epoxide and carbon monoxide under conditions to form a beta-lactone.25. The method of Embodiment 24 wherein the complex is dissolved or suspended in the coordinating compound utilized to form the complex.26. The method of Embodiment 24 or 25 wherein the epoxide corresponds to the formula:the beta-lactones correspond to the general formula:wherein:R3 is independently in each occurrence hydrogen or a carbon containing group which may have one or more hydrogen or fluorine atoms attached to the carbon atoms which may optionally contain one or more heteroatoms and / or substituents.27. The method of any one of Embodiments 24 to 26 wherein the complex formed is contacted with an epoxide and carbon monoxide in the presence of a liquid solvent.28. The method of embodiment 27, wherein the solvent is tetrahydrofuran, 2,5-dimethyl tetrahydrofuran, sulfolane, N-methyl pyrrolidone, 1 ,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ethers, methyl tertbutyl ether, diethylether, diphenyl ether, 1 ,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, dibasic esters, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxy ethane, acetone, methylethyl ketone, or mixture thereof.29. The method according to any one of Embodiments 26 to 28 wherein be R3is hydrogen, a halogen substituted alkyl group, a sulfonic acid substituted alkyloxy group; an alkyl sulfonate alkyloxy group; alkyl ether substituted alkyl group; a polyalkylene oxide substituted alkyl group, an alkyl ester substituted alkyl group; an alkenyloxy substituted alkyl group; an aryl ester substituted alkyl group; an alkenyl group; a cyano substituted alkyl group; an alkenyl ester substituted alkyl group; a cycloalkyl substituted alkyl group; an aryl group; a heteroatom containing cycloalkenyl, alkyl ether substituted alkyl group; a hydroxyl substituted alkyl group, a cycloaliphatic substituted alkenyl group; an aryl substituted alkyl group; a haloaryl substituted alkyl group; an aryloxy substituted alkyl group; an alkyl ether substituted alkaryl group; a hetero atom containing cycloaliphatic group substituted alkyl group; a hetero atom containing aryl substituted alkyl group, an alkyl amide substituted alkyl group, an alkenyl substituted cycloaliphatic group; two R1 may form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted with a beta propiolactone group which may optionally be contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutene substituted alkyl group, optionally substituted with one or more ether groups; with the proviso that one of the R1 on the beta carbon atom is hydrogen.30. The method of embodiment 29, wherein the solvent is tetrahydrofuran.31. The method of any one of Embodiments 24 to 30, wherein the method is performed in a continuously stirred reactor and the average residence time of the reaction mixture is about 5 minutes to about 240 minutes.32. The method of Embodiment 24 to 31 , wherein the average residence time of the reaction mixture is about 15 minutes to 120 minutes.Examples

[0060] The following examples are provided to illustrate the invention but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.

[0061] Example 1 . A 2-dram vial with stir bar is charged with 0.202 g (TPP)AIEt and 38 mg CoCI2. THF (4 mL) is added to the vial and the mixture is allowed to stir for 5 min. AIEt3 (0.65 mL of 1 M solution in hexanes) is added to the vial which is then placed in a pressure reactor and sealed. The reaction is pressurized with 450 psi carbon monoxide (CO) then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. The reaction mixture is layered with 4 mL heptane and allowed to sit overnight at room temperature. The resulting solid is filtered, washed with heptane, and dried under vacuum to afford a purple solid. The solid, useable as a catalyst, is tested for ethylene oxide (EO) conversion, which is illustrated in FIG. 1.

[0062] Example 2. A 2-dram vial with stir bar is charged with 119 mg CoCI2. THF (2 mL) is added to the vial and the mixture is allowed to stir for 5 min. AIEt3 (2.0 mL of 1 M solution in hexanes) is added to the vial which is then placed in a pressure reactor and sealed. The reaction is pressurized with 450 psi CO then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. A vial with 152 mg (TPP)AICI and THF (1 mL) is charged with 1 mL of the reaction mixture. The resulting mixture is allowed to stir for 2 h then layered with 2 mL heptane and allowed to sit overnight at room temperature. The resulting solid is filtered, washed with heptane, and dried under vacuum to afford a purple solid. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1 .

[0063] Example 3. A 2-dram vial with stir bar is charged with 0.202 g (TPP)AIEt and 52 mg Co(OAc)2. THF (3.4 mL) is added to the vial and the mixture is allowed to stir for 5 min. AIEt3 (0.65 mL of 1 M solution in hexanes) is added to the vial which is then placed in a pressure reactor and sealed. The reaction is pressurized with 180 psi CO then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. The reaction mixture is layered with 4 mL heptane and allowed to sit overnight at room temperature. The resulting solid is filtered, washed with heptane, and dried under vacuum to afford a purple solid. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1 .

[0064] Example 4. A 2-dram vial with stir bar is charged with 0.198 g (TPP)AIEt and 52 mg Co(OAc)2. THF (3.4 mL) is added to the vial and the mixture is allowed to stir for 5 min. AIEt3 (0.65 mL of 1 M solution in hexanes) is added to the vial which is then placed in a pressure reactorand sealed. The reaction is pressurized with 180 psi CO then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. The reaction mixture is layered with 4 mL heptane and allowed to sit overnight at room temperature. The resulting solid is filtered, washed with heptane, and dried under vacuum to afford a purple solid. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1 .

[0065] Example 5. A 2-dram vial with stir bar is charged with 0.097 g TPPH2 and 0.8 mL heptane. AIEt3 (0.52 mL of 1 M solution in heptane) is added. The mixture is stirred at room temperature for 2 h. THF (2.7 mL) and 28 mg Co(OAc)2 were added to the vial which is then placed in a pressure reactor and sealed. The reaction is pressurized with 450 psi CO then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. The resulting solid is filtered, washed with heptane, and dried under vacuum to afford a purple solid. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1.

[0066] FIG. 1 is an illustration of catalytic activity over time and conversion of EO for the catalysts formed according to Examples 1 -5. Catalyst (i.e., solid; 0.06 mol%) is dissolved in THF (70 mL) and added to a 150 mL shot tank. The solution is added to a 300 mL Parr reactor with 450 psi CO. The reactor is stirred and heated to 70 C. EO (approx.. 4 grams) is added to the reactor under 900 psi CO. The reaction is allowed to run until EO is consumed. EO conversion is calculated based on the amount of bPL formed, which is tracked by ReactIR. In the graph, 0.1 means 10% of EO is converted to bPL, 0.5 = 50% converted, etc.

Claims

CLAIMSWhat is Claimed is:

1. A method comprising: a) contacting a cobalt salt comprising one or more of a cobalt halide or ester with a trialkylaluminum or halodialkylaluminum in a coordinating compound and / or an inert solvent to form a solution; b) contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of from about 25 °C to about 100 °C under conditions to form cobalt carbonyl: and c) contacting the cobalt carbonyl with a porphyrin metal halide or alkyl and a coordinating compound, and optionally an inert solvent, under conditions to form a complex of a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.

2. The method of Claim 1 wherein molar ratio of the trialkylaluminum or halodialkylaluminum to the cobalt salt is 2.0 to 1 .0 or greater.

3. The method of Claim 1 or 2 wherein the inert solvent is a non-polar ether, aromatic solvent, or alkane.

4. The method of any one of Claims 1 to 3 wherein the coordinating compound and / or an inert solvent is diethyl ether, tetrahydrofuran, toluene, or heptane.

5. The method of any one of Claims 1 to 4 wherein the porphyrin metal halide or alkyl and cobalt carbonyl are contacted such that there is a molar excess of porphyrin metal halide or alkyl.

6. The method of any one of Claims 1 to 5 wherein the porphyrin metal halide or alkyl and cobalt carbonyl are contacted at a molar ratio of 2.

0. :1 or greater.

7. The method of any one of Claims 1 to 6 wherein an molar ratio or greater of the coordinating compound is contacted with porphyrin metal halide or alkyl.

8. A method comprising contacting: a) contacting a trialkylaluminum or halodialkylaluminum with a porphyrin ligand and in inert solvent to form a solution containing a porphyrin metal halide or alkyl;b) contacting the solution of with a cobalt salt comprising one or more of a cobalt halide or ester to make a formed solution; and, c) contacting the formed solution with carbon monoxide having a partial pressure of about 10 psi to about 500 psi pressure at a temperature of about 10 °C to about 120 °C in the presence of a coordinating compound under conditions to form a complex containing a cation of a porphyrin metal halide or alkyl wherein the coordinating compound is coordinated to the metal and an anion of cobalt carbonyl.

9. The method of Claim 8 wherein the molar ratio of the trialkylaluminum or halodialkylaluminum to cobalt salt is 3.0:1 .0 or greater.

10. The method of any one of Claim 8 or 9 wherein the inert solvent is an alkane or aromatic solvent.11 . Themethod of any one of Claims 8 to 10 the inert solvent is toluene, heptane, or a hexane.

12. The method of any one of Claims 8 to 11 wherein an equivalent excess of the trialkylaluminum or halodialkylaluminum is contacted with the tetraphenylporphyrin.

13. The method of any one of Claims 8 to 12 wherein the trialkylaluminum or halodialkylaluminum is contacted with the tetraphenylporphyrin at a molar ratio of about 3.0:1 .0 or greater.

14. The method of any one of Claims 8 to 13 wherein an equivalent excess of the coordinating compound is contacted with the porphyrin ligand.

15. The method of any of the preceding claims wherein the cobalt salt comprises one or more of a cobalt halide or cobalt ester.

16. The method of any of the preceding claims wherein the cobalt salt comprises a cobalt halide or a cobalt acetate17. The method of any of the preceding claims wherein the cobalt salt comprises one or more of cobalt chloride or cobalt acetate.

18. The method of any of the preceding claims wherein the porphyrin metal halide or alkyl compound corresponds to the formula;wherein:CS is separately in each occurrence a molecule of a coordinating compound;M1 is Al:R is separately at each occurrence hydrogen, halogen, -OR2, -NRy2, -SR, -CN, -NO2, - SO2Ry, -SORy, -SO2NRy2; -CNO, -NRSO2Ry, -NCO, -N3, -SIR2; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1 -20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;Ry is separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl, arylalkyl; 6 to 10 membered aryl; C1-12 aliphatic; C1 -12 heteroaliphatic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two Ry on the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4 to 7 membered heterocyclic ring having 0 to 2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;R1 and R2 are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted; and,X is separately in each occurrence is a halogen or alkyl.

19. The method of Claim 18 wherein:CS is separately in each occurrence a molecule of a dihydrocarbyl ether, alkylene ether or cyclic ether.R is separately at each occurrence hydrogen or alkyl,R1 and R2 are separately in each occurrence phenyl or substituted alkyl; and,X is separately in each occurrence is alkl, chlorine or bromine.

20. The method of Claim 19 wherein:CS is separately in each occurrence a molecule of a cyclic ether;R is separately at each occurrence hydrogen.R1 is separately in each occurrence an optionally substituted phenyl group or an optionally substituted alkyl group; and,X is separately in each occurrence is ethyl, chlorine or bromine.

21. The method of any one of the preceding claims wherein the coordinating compound is a dihydrocarbyl ether, a polyalkylene oxide or a cyclic ether.

22. The method of any one of the preceding claims wherein the coordinating compound is a cyclic ether.

23. The method of any one of the preceding claims wherein the coordinating compound is dioxane or tetrahydrofuran.

24. The method of any one of the preceding claims wherein the complex formed is contacted with an epoxide and carbon monoxide under conditions to form a beta-lactone.

25. The method of Claim 24 wherein the complex is dissolved or suspended in the coordinating compound utilized to form the complex.

26. The method of Claim 24 or 25 wherein the epoxide corresponds to the formula:the beta-lactones correspond to the general formula:wherein:R3 is independently in each occurrence hydrogen or a carbon containing group which may have one or more hydrogen or fluorine atoms attached to the carbon atoms which may optionally contain one or more heteroatoms and / or substituents.

27. The method of any one of Claims 24 to 26 wherein the complex formed is contacted with an epoxide and carbon monoxide in the presence of a liquid solvent.

28. The method of claim 27, wherein the solvent is tetrahydrofuran, 2,5-dimethyl tetrahydrofuran, sulfolane, N-methyl pyrrolidone, 1 ,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ethers, methyl tertbutyl ether, diethylether, diphenyl ether, 1 ,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, dibasic esters, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxy ethane, acetone, methylethyl ketone, or mixture thereof.

29. The method according to any one of Claims 26 to 28 wherein be R3is hydrogen, a halogen substituted alkyl group, a sulfonic acid substituted alkyloxy group; an alkyl sulfonate alkyloxy group; alkyl ether substituted alkyl group; a polyalkylene oxide substituted alkyl group, an alkyl ester substituted alkyl group; an alkenyloxy substituted alkyl group; an aryl ester substituted alkyl group; an alkenyl group; a cyano substituted alkyl group; an alkenyl ester substituted alkyl group; a cycloalkyl substituted alkyl group; an aryl group; a heteroatom containing cycloalkenyl, alkyl ether substituted alkyl group; a hydroxyl substituted alkyl group, a cycloaliphatic substituted alkenyl group; an aryl substituted alkyl group; a haloaryl substituted alkyl group; an aryloxy substituted alkyl group; an alkyl ether substituted alkaryl group; a hetero atom containing cycloaliphatic group substituted alkyl group; a hetero atom containing aryl substituted alkyl group, an alkyl amide substituted alkyl group, an alkenyl substituted cycloaliphatic group; two R1 may form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted with a beta propiolactone group which may optionally be contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutene substituted alkyl group, optionally substituted with one or more ether groups; with the proviso that one of the R1 on the beta carbon atom is hydrogen.

30. The method of claim 29, wherein the solvent is tetrahydrofuran.31 . The method of any one of Claims 24 to 30, wherein the method is performed in a continuously stirred reactor and the average residence time of the reaction mixture is about 5 minutes to about 240 minutes.

32. The method of Claim 24 to 31 , wherein the average residence time of the reaction mixture is about 15 minutes to 120 minutes.

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