Hydroformylation catalysts comprising fluorophosphine ligands and their precursors

Abstract

The present invention relates to compositions comprising compounds having the formula M2(CO) m (PF3) n which can be used as hydroformylation pre-catalysts for the conversion (e.g., hydroformylation) of olefin feeds, particularly feeds containing internal olefins and highly branched complex feeds, where M is a Group 9 metal (such as cobalt), m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

Description

[0001] Inventors: Alex E. Carpenter, Danielle G. Singleton, and Sarah A. Kheir

[0002] Priority

[0003] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 003,600, filed on April 1, 2020, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0004] The present invention generally relates to hydroformylation, and more particularly, to Group 9 metal complexes modified with one or more fluorophosphine ligands, which can effectively promote hydroformylation at high syngas pressures. Background Art

[0005] In the presence of a hydroformylation catalyst, a hydroformylation reaction forms an oxygenated organic compound (such as an aldehyde or an alcohol) by reacting a mixture of carbon monoxide and hydrogen, such as synthesis gas (“syngas”), with one or more olefins. This process is commonly referred to as the Oxo Process. Typical hydroformylation catalysts include those based on cobalt or rhodium chemistry. Generally, the initial reaction product formed after hydroformylation is an aldehyde having one more carbon atom in its molecular structure than the olefin from which it is produced. The aldehyde initially produced after hydroformylation is typically reduced to the corresponding alcohol by hydrogenation for ease of processing and further use. Alternatively, it can be oxidized to the corresponding carboxylic acid.

[0006] For example, long-chain alcohols can be prepared by hydroformylation of the corresponding olefins followed by reduction. Long-chain branched alcohols or functionalized products formed therefrom can be used in many applications due to their amphiphilic properties and biodegradability. Long-chain alcohols or functionalized products formed therefrom can be used as surfactants, emollients, lubricants, coatings, wetting agents, corrosion inhibitors, synthetic bases, and / or therapeutic delivery agents. Unfortunately, highly branched olefins generally react poorly under typical hydroformylation reaction conditions.

[0007] Certain hydroformylation catalysts can be used to prepare long-chain, substantially unbranched alcohols using feedstocks capped with vinyl groups on the carbon chain, such as linear α-olefins or linear α-olefin oligomers. The conversion of the vinyl olefin moiety to an alcohol moiety by hydroformylation and subsequent reduction generally preserves the linearity or degree of branching of the carbon chain without introducing new branches and results in the alcohol moiety being located at or near the end of the carbon chain.

[0008] Cobalt hydride carbonyl compounds, such as HCo(CO)4, are used as hydroformylation catalysts in many cases. The inherent volatility of HCo(CO)4 allows for the use of stripping gases to recover it, as described in U.S. Patent No. 4,625,067 and U.S. Patent No. 5,237,105. One problem associated with the use of HCo(CO)4 in hydroformylation is cobalt plating, which is due to the inherent instability of HCo(CO)4 in the absence of a high CO partial pressure. Attempts have been made to modify the phosphine of cobalt hydride carbonyl compounds to alter their catalytic properties and facilitate improved handling. U.S. Patent 4,070,403 describes the use of HCo(CO)4 modified with phosphine ligands for carrying out hydroformylation reactions. Other references employing phosphine modification of cobalt hydride carbonyl hydroformylation catalysts include U.S. Patent US 3,624,158; US 3,418,351; US 3,278,612; and French Patent 1389699. A common theme in phosphine-modified hydroformylation catalyst systems is to drive lower pressure process conditions and achieve greater selectivity for linear products. This significantly increases catalyst complexity, reduces the tolerance of the catalyst system to complex / branched feeds, and reduces the accompanying volatility of the catalyst system.

[0009] As noted above, HCo(CO)4 tends to decompose in the absence of a high carbon monoxide pressure. In addition, this hydroformylation catalyst typically produces excessive amounts of paraffinic hydrocarbons and heavy by-products. Thus, high syngas pressures are often used during cobalt-mediated hydroformylation reactions. However, since conventional phosphine ligands tend to be displaced by carbon monoxide, especially at high syngas pressures, phosphine modification of HCo(CO)4 with conventional phosphine ligands to alter catalytic properties can be problematic in this regard. In addition, phosphine modification tends to reduce the volatility of the parent HCo(CO)4 compound, making catalyst recycle significantly more difficult than when phosphine modification is not used.

[0010] The trifluorophosphine-modified cobalt hydride complex is separable due to the high affinity of the PF3 ligand for cobalt, and as a result, it exhibits much higher thermal stability than other phosphine-modified cobalt hydride complexes. The use of these types of phosphine-modified cobalt complexes in hydroformylation is currently unknown. Interesting references describing the isolated trifluorophosphine-modified cobalt hydride complex include "Cobalt-catalyzed hydroformylation of alkenes: generation and recycling of the carbonyl species, and catalytic cycle" by Hebrard, F. et al. (2009), Chem. Rev., v. 109(9), pp. 4272-4282; Inorg. Chem., v. 9, pp. 2403-2407 by Frenz, B.A. (1970); Angew. Chem. Int. Ed., v. 4, p. 148 by Kruck, T. et al. (1965); Angew. Chem. Int. Ed., v. 4, p. 870 by Kruck, T. et al. (1965); and Angew. Chem. Int. Ed., v. 6, pp. 53-67 by Kruck, T. (1967).

[0011] Other interesting references include: "[1,1-Co2(CO)6(CNAr Mes2 )2]: A Structural Mimic of the Elusive D 2d Isomer of [Co2(CO)8]" by Carpenter, A.E. et al. (2013), Chem. Eur. J., v. 19, pp. 10452-10457. Summary of the Invention

[0013] The present invention relates to compounds and compositions comprising a compound having the formula M2(CO) m (PF3) n wherein M is a Group 9 metal, m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

[0014] The present invention also relates to a catalyst system comprising hydrogen and the reaction product of a compound having the formula M2(CO) m (PF3) n wherein M is a Group 9 metal, m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

[0015] The present invention also provides a method of contacting an olefin with carbon monoxide and hydrogen, such as syngas, and a pre-catalyst comprising the reaction product of M2(CO) m m with (PF3) (such as Co2(CO)8 and PF3), under conditions effective to convert the olefin to a hydroformylation reaction product, where M is a Group 9 metal and m is 1, 2, 3, 4, 5, 6 or 7.

[0016] Other methods provided herein include forming an active hydroformylation catalyst having the formula HCo(CO) m′ m′ (PF3) n′ n′ where m′ is 1, 2 or 3, n′ is 1, 2 or 3, and the sum of m′ and n′ is 4; and contacting an olefin with the active hydroformylation catalyst and syngas under conditions effective to convert the olefin to a hydroformylation reaction product.

[0017] In addition, the present invention relates to recovering a hydroformylation catalyst or a waste form thereof and transporting the recovered catalyst to an upstream location for recycle / reuse. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The following drawings are included to illustrate certain aspects of the present disclosure and should not be considered exclusive embodiments. The disclosed subject matter is capable of considerable modification, alteration, combination, and equivalents in form and function, as will occur to those ordinarily skilled in the art having the benefit of this disclosure.

[0019] Figure 1 Shows the attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectrum of the reaction product of Example 1.

[0020] Figure 2 Shows the ATR-FTIR spectrum of the reaction product of Example 1, superimposed on the simulated IR spectra of two possible Co2(CO)4(PF3)4 isomers.

[0021] Figure 3 Shows the 19 F NMR spectrum of the reaction product of Example 1.

[0022] Figure 4 Shows the 31 P{ 1 H} NMR spectrum of the reaction product of Example 1.

[0023] Figure 5 Shows the 13 C{ 1 H} NMR spectrum of the reaction product of Example 1.

[0024] Figures 6 - 8 Shows a schematic gas chromatogram of the hydroformylation reaction products obtained from Entries 1 - 3 in Example 2, respectively.

[0025] Figure 9A and 9B shows an image of the plating residue caused by using a conventional hydroformylation catalyst ( Figure 9A ) relative to the plating residue caused by using Co2(CO)4(PF3)4 ( Figure 9B ).

[0026] Figure 10 Shows a schematic gas chromatogram of the hydroformylation reaction product obtained from Example 3.

[0027] DETAILED DESCRIPTION

[0028] The disclosure of the present invention generally relates to hydroformylation, and more particularly, to hydroformylation catalyst precursors and catalyst systems comprising a Group 9 metal complex modified with trifluorophosphine and methods of hydroformylating therewith.

[0029] There are currently problems associated with the phosphine modification of cobalt hydride carbonyl complexes used for hydroformylation. In particular, phosphine modification can limit the volatility of the catalyst used to facilitate recycling. In addition, at high syngas pressures, conventional phosphines can be readily displaced by carbon monoxide. Because of this, it is currently relatively difficult to alter the catalytic properties and other performance characteristics of cobalt hydride carbonyl compounds, particularly at elevated CO partial pressures where phosphine ligands are typically readily displaced.

[0030] The disclosure of the present invention provides a trifluorophosphine - modified Group 9 metal complex that can be effectively converted into an active hydroformylation catalyst under hydroformylation reaction conditions. Advantageously, the active hydroformylation catalyst can maintain significant volatility to facilitate its recycling and provide a different product distribution compared to conventional phosphine - modified cobalt hydride carbonyl compounds. Without wishing to be bound by theory, it is believed that these advantageous properties result from the retention of at least one trifluorophosphine ligand in the active hydroformylation catalyst. In particular, the active hydroformylation catalyst produced according to the disclosure herein can convert olefins into hydroformylation reaction products with a higher degree of branching than can be obtained with conventional phosphine - modified hydroformylation catalysts. In addition, the active hydroformylation catalyst disclosed herein can avoid the adverse effects of cobalt plating that typically occur in the case of unmodified cobalt hydride carbonyl complexes, which can facilitate a relatively simple catalyst recycling process. As the incidence of cobalt plating is reduced, significantly less plant downtime can be achieved compared to unmodified cobalt hydride carbonyl complexes.

[0031] Advantageously, the active hydroformylation catalysts disclosed herein can be formed in situ under hydroformylation reaction conditions from readily preparable trifluorophosphine-modified dimeric Group 9 metal complexes, particularly at high syngas pressures of about 1,000 psi or higher. Due to the strong bonding between the cobalt center and the trifluorophosphine ligand, it is believed that the trifluorophosphine ligand remains in the active hydroformylation catalyst to provide particularly advantageous properties such as tolerance to both linear and branched olefin feeds and a low tendency to cobalt plating. Further advantageously, the dimeric Group 9 metal complexes disclosed herein are liquids and can be used under conditions similar to those used for liquid cobalt carbonyl complexes in the hydroformylation reaction. More specific disclosure regarding the dimeric Group 9 metal complexes and the active hydroformylation catalysts formed therefrom is provided below.

[0032] Other process advantages can also be achieved using trifluorophosphine-modified hydroformylation catalysts. As described in U.S. Patent Application Publication U.S. 2005 / 0119508, the cobalt flash process requires the use of auxiliary cobalt recovery after the vapor-phase recovery of volatile cobalt carbonyls (e.g., HCo(CO)4 / Co2(CO)8) in a stripping reactor. In part, due to the tendency of HCo(CO)4 to decompose into cobalt metal and less volatile cobalt-containing compounds, oxidative aqueous recovery is necessary. The high binding affinity of cobalt for trifluorophosphine and the enhanced stability of the cobalt compounds containing trifluorophosphine enable the optional use of a stripping reactor to remove cobalt from the crude hydroformylation product stream in the present disclosure. Thus, a stripping reactor with improved efficiency relative to HCo(CO)4 can be used to recover the trifluorophosphine-modified cobalt hydroformylation catalyst.

[0033] Definitions

[0034] All numerical values in the detailed description and claims herein are modified by the term “about” or “approximately” relative to the indicated values, and account for experimental error and variations that would be expected by a person of ordinary skill in the art. Unless otherwise indicated, room temperature is about 23 °C.

[0035] As used in the present disclosure and claims, the singular forms “a,” “an,” and “the” include plural forms unless the context clearly dictates otherwise.

[0036] For the purposes of the present disclosure, a new numbering scheme for the periodic table groups is used. In said numbering scheme, the groups (columns) are numbered sequentially from 1 to 18 from left to right, excluding the f-block elements (lanthanides and actinides). Under this scheme, Co, Rh, Ir, and Mt are Group 9 transition metals.

[0037] The terms “group,” “radical,” and “substituent” are used interchangeably herein.

[0038] Unless otherwise indicated, reference to a group without specifying its particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclobutyl).

[0039] The term "hydrocarbon" refers to a class of compounds having hydrogen bonded to carbon and includes saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, and mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms. The term "C n n" refers to a hydrocarbon or hydrocarbon radical having n carbon atoms per molecule or group, where n is a positive integer. Such hydrocarbon compounds can be one or more of straight-chain, branched-chain, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic. A cyclic hydrocarbon as used herein may be referred to as a "carbocycle" and includes saturated, unsaturated, and partially unsaturated carbocyclic compounds, as well as aromatic carbocyclic compounds. The term "heterocycle" refers to a carbocycle containing at least one ring heteroatom.

[0040] The terms "hydrocarbyl radical", "hydrocarbyl group", or "hydrocarbyl" may be used interchangeably and are defined to represent a group consisting of only hydrogen and carbon atoms and which bears at least one unfilled valence position when removed from a parent compound. A hydrocarbyl can be saturated or unsaturated, straight-chain or branched-chain, cyclic or acyclic, aromatic or non-aromatic. Preferred hydrocarbyls include C1-C 100 groups which can be straight-chain or branched-chain. Examples of such groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-pentyl (isopentyl), hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. The term "hydrocarbyl having from 1 to about 100 carbon atoms" refers to a moiety selected from straight-chain, cyclic, or branched-chain C1-C 100 hydrocarbyls.

[0041] The term "optionally substituted" means that a group can be unsubstituted or substituted. For example, the term "optionally substituted hydrocarbyl" means that at least one hydrogen atom or carbon atom in the hydrocarbyl is replaced with a heteroatom or heteroatom functional group. Unless otherwise indicated, any hydrocarbyl herein can be optionally substituted.

[0042] The term "straight-chain" or "straight-chain hydrocarbon" refers to a hydrocarbon or hydrocarbon radical having a continuous carbon chain without side-chain branching.

[0043] The term "branched-chain" or "branched-chain hydrocarbon" refers to a hydrocarbon or hydrocarbon radical having a straight-chain carbon chain or carbocycle, wherein a hydrocarbyl side chain extends from the straight-chain carbon chain or carbocycle.

[0044] The term "saturated" or "saturated hydrocarbon" refers to a hydrocarbon or hydrocarbon radical in which all carbon atoms are bonded to four other atoms, except where an unfilled valence position exists on a carbon in the hydrocarbyl.

[0045] The term "unsaturated" or "unsaturated hydrocarbon" refers to a hydrocarbon or hydrocarbon radical in which one or more carbon atoms are bonded to fewer than four other atoms, excluding the open valence positions on the carbon atoms present. That is, the term "unsaturated" refers to a hydrocarbon or hydrocarbon radical having one or more double bonds and / or triple bonds, where the double bond and / or triple bond is between two carbon atoms and / or between a carbon atom and a heteroatom.

[0046] The terms "alkyl radical" and "alkyl" are used interchangeably in the disclosure of the present invention and refer to a hydrocarbon radical that does not have an unsaturated carbon-carbon bond and that may optionally be substituted. The alkyl group can be straight-chain, branched-chain, cyclic, or a combination thereof. "Alkyl radical" is defined as a C1-C 100 alkyl. Examples of such groups can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. A substituted alkyl group is a group in which at least one hydrogen atom of the alkyl group has been replaced by at least one non-hydrogen group, which non-hydrogen group is, for example, a hydrocarbon radical, a heteroatom, or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*, -SiR*3, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, etc., where each R* is independently a hydrocarbon radical or a halogenated hydrocarbon radical, and two or more R*s can be joined together to form a substituted or unsubstituted saturated hydrocarbon radical, a partially unsaturated or aromatic cyclic or polycyclic structure, or a structure in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0047] The term "branched-chain alkyl" refers to an alkyl group containing a tertiary carbon or a quaternary carbon (a tertiary carbon is a carbon atom bonded to three other carbon atoms, and a quaternary carbon is a carbon atom bonded to four other carbon atoms). For example, 3,5,5-trimethylhexylphenyl is an alkyl group (hexyl) having three methyl branches (thus, one tertiary carbon and one quaternary carbon), and thus is a branched-chain alkyl group bonded to the phenyl group.

[0048] The terms "cycloalkyl" or "cycloalkyl group" are used interchangeably to refer to a saturated hydrocarbon radical in which the carbon atoms form one or more ring structures. The terms "cycloalkenyl" or "cycloalkenyl group" are used interchangeably to refer to a cyclic hydrocarbon radical group containing a carbon-carbon double bond in the ring.

[0049] The terms "alkene" and "olefin" are used synonymously herein. Similarly, the terms "alkenic" and "olefinic" are used synonymously herein. Unless otherwise specified, these terms encompass all possible geometric isomers. The term "alkenyl" refers to a hydrocarbyl group having a carbon-carbon double bond. The alkenyl group can be straight-chain, branched-chain or cyclic, and contains one or more carbon-carbon double bonds. The alkenyl group can be optionally substituted. Examples of alkenyl groups can include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, etc.

[0050] The term "arylalkene" refers to an aryl group in which a hydrogen atom has been replaced by an alkenyl group or a substituted alkenyl group. For example, styrylindenyl is an indene substituted by an arylalkene (styryl group).

[0051] The carbon-carbon double bond in an alkene can be in various structural or geometric isomeric forms, which can include ethylidene, vinyl, disubstituted vinylidene and trisubstituted vinylidene.

[0052] The term "vinyl" (also known as "vinyl alkene") refers to an alkene represented by the following formula:

[0053]

[0054] wherein R is a hydrocarbyl group, preferably a saturated hydrocarbyl group such as an alkyl group.

[0055] The term "ethylidene" (also known as "ethylidene alkene") refers to an alkene represented by the following formula:

[0056]

[0057] wherein each R is independently selected hydrocarbyl group, preferably a saturated hydrocarbyl group such as an alkyl group. Ethylidene is a 1,1-disubstituted vinylidene group.

[0058] The term "disubstituted vinylidene" (also known as "disubstituted ethylidene alkene") refers to

[0059] (i) an alkene represented by the following formula

[0060]

[0061] (ii) an alkene represented by the following formula

[0062]

[0063] (iii) any proportion mixture thereof,

[0064] Each R is independently a hydrocarbon group, preferably a saturated hydrocarbon group such as an alkyl group. The term "disubstituted vinylidene" does not include the term "ethylidene". That is, disubstituted vinylidene only represents 1,2-disubstituted vinylidene and does not include ethylidene.

[0065] The term "trisubstituted vinylidene" (also referred to as "trisubstituted olefin") refers to an olefin represented by the following formula:

[0066]

[0067] wherein each R is independently a hydrocarbon group, preferably a saturated hydrocarbon group such as an alkyl group. Alternatively, two R groups on adjacent carbon atoms can together form a non-aromatic ring structure, and the third R group remains as a side-chain hydrocarbon group.

[0068] The term "tetrasubstituted olefin" refers to an olefin represented by the following formula:

[0069]

[0070] wherein each R is independently a hydrocarbon group, preferably a saturated hydrocarbon group such as an alkyl group. Alternatively, two R groups on adjacent carbon atoms can together form a non-aromatic ring structure.

[0071] The term "α-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure (R″HC=CH2, where R″ is hydrogen or a hydrocarbon group, preferably R″ is an alkyl group). Non-limiting examples of α-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane. In the disclosure of the present invention, any of these α-olefins can undergo hydroformylation.

[0072] In the disclosure of the present invention, ethylene should be regarded as an α-olefin.

[0073] "Polymer" has two or more identical or different monomer units. "Homopolymer" is a polymer having the same monomer units. "Copolymer" is a polymer having two or more monomer units different from each other. An oligomer is generally a polymer (homopolymer or copolymer) having 2 to 100 monomer units. "Different" as used to refer to monomer units means that the monomer units differ from each other by at least one atom or are isomeric different.

[0074] Hydroformylation catalyst

[0075] The active hydroformylation catalyst of the present disclosure can be formed from a catalyst precursor (also referred to as a pre-catalyst) comprising the reaction product of Co2(CO)8 and PF3, and the catalyst precursor is preferably a compound having Formula 1:

[0076] M2(CO) m (PF3) n

[0077] Formula 1

[0078] where each M is a Group 9 metal (such as Co or Rh), m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8. Preferably, M is cobalt. Preferably, m is 2 or greater. In particular, m can be 2, 3, 4, 5, 6 or 7, and n can be 1, 2, 3, 4, 5 or 6. More preferably, both m and n are 4. Any single dimeric Group 9 metal complex or mixture of dimeric Group 9 metal complexes can be present in the compositions disclosed herein, wherein the dimeric Group 9 metal complex can be bridged by carbon monoxide ligands or contain a direct metal-metal bond.

[0079] Certain dimeric Group 9 metal complexes disclosed herein are believed to contain one or more bridging carbon monoxide groups (ligands) in addition to other non-bridging ligands. In particular, the bridged dimeric Group 9 metal complexes of the present disclosure are believed to contain two bridging carbon monoxide groups, each between a first metal center and a second metal center, preferably between a first cobalt center and a second cobalt center. In one particular instance, the dimeric Group 9 metal complex of the present invention can have a structure represented by Formula 2:

[0080]

[0081] where L 1 、L 2 、L 3 、L 4 、L 5 and L 6 are independently CO or PF3, provided that L 1 、L 2and L 3 at least one of which is CO, L 4 , L 5 and L 6 at least one of which is CO, and L 1 , L 2 , L 3 , L 4 , L 5 and L 6 at least one of which is PF3. Preferably, L 1 -L 6 at least one of which is PF3, and any L 1 -L 6 that is not PF3 is CO. The specific dimeric Group 9 metal complex defined by Formula 2 may include:

[0082] a) L 1 -L 6 at least one of which is CO, and any L 1 -L 6 that is not CO is PF3, provided that L 1 -L 6 at least one of which is PF3;

[0083] b) L 1 -L 6 at least two of which are CO, and any L 1 -L 6 that is not CO is PF3, provided that L 1 -L 6 at least one of which is PF3;

[0084] c) L 1 -L 6 at least three of which are CO, and any L 1 -L 6 that is not CO is PF3, provided that L 1 -L 6 at least one of which is PF3;

[0085] d) L 1 -L 6 at least four of which are CO, and any L 1 -L 6 that is not CO is PF3, provided that L 1 -L 6 at least one of which is PF3;

[0086] e) L 1 -L 6 five of which are CO, and L 1 -L6 One of them is PF3;

[0087] f) L 1 、L 2 and L 3 One of them is CO, and any L that is not CO 1 -L 6 is PF3, provided that L 1 -L 6 at least one of them is PF3;

[0088] g) L 1 、L 2 and L 3 Two of them are CO, and any L that is not CO 1 -L 6 is PF3, provided that L 1 -L 6 at least one of them is PF3;

[0089] h) L 1 、L 2 and L 3 Three of them are CO, and any L that is not CO 1 -L 6 is PF3, provided that L 1 -L 6 at least one of them is PF3;

[0090] i) L 1 、L 2 and L 3 at least one of them is CO, L 4 、L 5 and L 6 at least one of them is CO, and any L that is not CO 1 -L 6 is PF3, provided that L 1 -L 6 at least one of them is PF3;

[0091] j) L 1 、L 2 and L 3 at least two of them are CO, L 4 、L 5 and L 6 at least one of them is CO, and any L that is not CO 1 -L 6 is PF3, provided that L 1 -L 6 at least one of them is PF3;

[0092] k) L1 , L 2 and L 3 at least two of which are CO, L 4 , L 5 and L 6 at least two of which are CO, and any L that is not CO 1 -L 6 is PF3, provided that L 1 -L 6 at least one of which is PF3;

[0093] l) L 1 , L 2 and L 3 each of which is CO, L 4 , L 5 and L 6 at least one of which is CO, and any L that is not CO 4 -L 6 is PF3, provided that L 4 -L 6 at least one of which is PF3; and

[0094] m) L 1 , L 2 and L 3 each of which is CO, L 4 , L 5 and L 6 two of which are CO, and L 4 -L 6 one of which is PF3.

[0095] The compound represented by Formula 2 can be a fused square pyramid geometry around each cobalt center. In the dimeric Group 9 metal complex represented by Formula 2, any CO group and any PF3 group can be in axial positions and / or in equatorial positions, which can fluctuate rapidly between isomeric positions, e.g., as described for other carbonyl cobalt complexes in Carpenter, A.E. et al. (2013) "[1,1-Co2(CO)6(CNAr Mes2 )2]: A Structural Mimic of the Elusive D 2d Isomer of [Co2(CO)8]", Chem. Eur. J., Vol. 19, pp. 10452-10457.

[0096] In another specific instance, the dimeric Group 9 metal complex of the present disclosure may comprise one or more metal bridging structures represented by Formulas 3A and 3B below,

[0097]

[0098] Among them, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 and L 8 are independently CO or PF3, and at least one of L 1 -L 8 is PF3, and any L 1 -L 8 that is not PF3 is CO. These Group 9 metal complexes may be characterized by a trigonal bipyramidal or distorted trigonal bipyramidal geometry around the cobalt center. In the dimeric Group 9 metal complexes represented by Formulas 3A and 3B, any CO group and any PF3 group may be in axial positions and / or in equatorial positions. Specific dimeric Group 9 metal complexes defined by Formulas 3A and 3B may include:

[0099] a) At least one of L 1 -L 8 is CO, and any L 1 -L 8 that is not CO is PF3, provided that at least one of L 1 -L 8 is PF3;

[0100] b) At least two of L 1 -L 8 are CO, and any L 1 -L 8 that is not CO is PF3, provided that at least one of L 1 -L 8 is PF3;

[0101] c) At least three of L 1 -L 8 are CO, and any L 1 -L 8 that is not CO is PF3, provided that at least one of L 1 -L 8 is PF3;

[0102] d) At least four of L 1 -L 8 are CO, and any L 1 -L 8 that is not CO is PF3, provided that at least one of L 1 -L 8 is PF3;

[0103] e) At least five of the L 1 -L 8 are CO, and any L that is not CO 1 -L 8 is PF3, provided that at least one of the L 1 -L 8 is PF3;

[0104] f) At least six of the L 1 -L 8 are CO, and any L that is not CO 1 -L 8 is PF3, provided that at least one of the L 1 -L 8 is PF3;

[0105] g) Seven of the L 1 -L 8 are CO, and one L that is not CO 1 -L 8 is PF3;

[0106] h) One of the L 1 -L 3 and the L 8 is CO, and any L that is not CO 1 -L 8 is PF3, provided that at least one of the L 1 -L 8 is PF3;

[0107] i) Two of the L 1 -L 3 and the L 8 are CO, and any L that is not CO 1 -L 8 is PF3, provided that at least one of the L 1 -L 8 is PF3;

[0108] j) Three of the L 1 -L 3 and the L 8 are CO, and any L that is not CO 1 -L 8 is PF3, provided that at least one of the L 1 -L 8 is PF3;

[0109] k) Two of the L 1 -L 3 and the L 8is CO and any L that is not CO 4 -L 7 is PF3 provided that L 4 -L 7 at least one of which is PF3;

[0110] l) L 1 、L 2 、L 3 、and L 8 at least one of which is CO, L 4 -L 7 at least one of which is CO and any L that is not CO 1 -L 8 is PF3 provided that L 1 -L 8 at least one of which is PF3;

[0111] m) L 1 、L 2 、L 3 、and L 8 at least two of which are CO, L 4 -L 7 at least one of which is CO and any L that is not CO 1 -L 8 is PF3 provided that L 1 -L 8 at least one of which is PF3;

[0112] n) L 1 、L 2 、L 3 、and L 8 at least two of which are CO, L 4 -L 7 at least two of which are CO and any L that is not CO 1 -L 8 is PF3 provided that L 1 -L 8 at least one of which is PF3;

[0113] o) L 1 、L 2 、L 3 、and L 8 at least three of which are CO, L 4 -L 7 at least one of which is CO and any L that is not CO 1 -L 8 is PF3 provided that L 1 -L 8 at least one of which is PF3;

[0114] p)L 1 , L 2 , L 3 , and L 8 At least three of them are CO, L 4 -L 7 At least two of them are CO and none of the L of CO 1 -L 8 is PF3, condition is L 1 -L 8 At least one of them is PF3;

[0115] q)L 1 , L 2 , L 3 , and L 8 At least three of them are CO, L 4 -L 7 At least three of them are CO and none of them is L of CO 1 -L 8 is PF3, condition is L 1 -L 8 At least one of them is PF3;

[0116] r)L 1 , L 2 , L 3 , and L 8 Each is CO, L 4 -L 7 At least one of them is CO, and none of the L 4 -L 7 is PF3, condition is L 1 -L 8 At least one of them is PF3;

[0117] s)L 1 , L 2 , L 3 , and L 8 Each is CO, L 4 -L 7 At least two of them are CO and none of the L of CO 4 -L 7 is PF3, condition is L 1 -L 8 At least one of them is PF3; and

[0118] t)L 1 , L 2 , L 3 , and L 8 Each is CO, L 4 -L7 Three of them are CO, and L 4 -L 7 One of them is PF3.

[0119] Referring again to Formulas 1, 2, 3A, and 3B, the combinations of variables m and n that apply include the following m, n pairs: 7, 1; 6, 2; 5, 3; 4, 4; 3, 5; 2, 6; and 7, 1. In a specific instance applicable to Formulas 1 and 2, m and n are each 4, in which case L 1 、L 2 and L 3 Two of them can be PF3, and L 1 、L 2 and L 3 One of them can be CO, and L 4 、L 5 and L 6 Two of them can be PF3, and L 4 、L 5 and L 6 One of them can be CO.

[0120] The present invention also relates to a catalyst system comprising the reaction product of hydrogen with one or more of the compounds represented by 1, 2, 3A, and 3B and any variants thereof described herein. Preferably, the catalyst system comprises the reaction product of hydrogen and a compound having the formula M2(CO) m (PF3) n wherein M is a Group 9 metal (preferably M is Co), m is 1, 2, 3, 4, 5, 6, or 7, n is 1, 2, 3, 4, 5, 6, or 7, and the sum of m and n is 8. Hydrogen can be provided to the catalyst system as hydrogen gas, as syngas, or any other hydrogen source that provides hydrogen for reaction with the precatalyst compound.

[0121] Hydrogen and the precatalyst compound are typically mixed in a ratio such that at least 1 equivalent of hydrogen is provided for each precatalyst molecule. Preferably, a large excess of hydrogen is used (i.e., 10, 100, 1000, 10,0000, 100,000, 100,000,000 equivalents).

[0122] Preferably, under hydroformylation reaction conditions, the dimeric Group 9 metal complex of the present disclosure is converted into an active catalytic species (active hydroformylation catalyst) and promotes the conversion of the olefin feed into the hydroformylation reaction product. The active catalytic species can represent the reaction product of the dimeric Group 9 metal complex and hydrogen (e.g., from syngas). Without wishing to be bound by theory, it is believed that the active catalytic species formed under hydroformylation reaction conditions can be represented by Formula 4:

[0123] HM(CO)m′ (PF3) n′

[0124] Formula 4

[0125] wherein M is a Group 9 metal, m′ is 1, 2, or 3, n′ is 1, 2, or 3, and the sum of m′ and n′ is 4. Preferably, M is cobalt. Preferably, m′ is 1 or greater. In particular, m′ is 1 or 2 and / or n′ is 1 or 2. More preferably, both m′ and n′ are 2.

[0126] Combinations of variables m′ and n′ applicable to Formula 4 include the following m′, n′ pairs: 3, 1; 2, 2; and 1, 3. The carbon monoxide and PF3 groups can be in any available axial or equatorial positions around the metal center.

[0127] The dimeric Group 9 metal complexes of the present disclosure are effective precatalysts for forming (optionally in situ under hydroformylation reaction conditions) a catalyst system as described herein, wherein the catalyst system exhibits improved stability (e.g., does not decompose) at a CO partial pressure of less than 1,500 psig (10 MPa), such as less than 1,000 psig (6.9 MPa), relative to a cobalt catalyst system of HCo(CO)4 and hydrogen under the same hydroformylation reaction conditions. Alternatively, the catalyst system is stable at a temperature of 80 °C or higher (such as 100 °C or higher). Alternatively, the catalyst system is stable at a temperature of 100 °C or higher (such as 120 °C or higher) and a CO partial pressure of less than 1,500 psig (10 MPa), such as less than 1,000 psig (6.9 MPa). "Does not decompose" means that the metal compound in the catalyst system, such as a cobalt compound, does not provide a significant amount of Group 9 metal (such as cobalt) precipitate ("metal plating") during the hydroformylation reaction, as shown by particles separable by filtering the product (e.g., Group 9 metal (such as cobalt) particles). Preferably, when tested under the same hydroformylation reaction conditions, the catalyst system described herein does not produce a hydroformylation reaction product having more Group 9 metal (such as cobalt) precipitate per gram compared to a catalyst system consisting essentially of the reaction product of HCo(CO)4 and hydrogen (hereinafter referred to as the "reference catalyst system"). Preferably, when tested under the same hydroformylation reaction conditions, the catalyst system produces less (such as 10%, or 20% or less, or 50% or less, 70%, or 80% or less, 90%, or 95% or less, 99%) Group 9 metal (such as cobalt) precipitate per gram than the reference catalyst system (as defined above). For the avoidance of doubt, the reactant feed ratio is considered to be part of the reaction conditions.

[0128] Preferably, the catalyst system formed herein is liquid at a temperature of 10 °C or higher (such as 20 °C or higher, such as 30 °C or higher). Preferably, the catalyst system formed herein is liquid at a CO partial pressure of 6.9 MPa or higher, or 10 MPa or higher. Preferably, the catalyst system formed herein is liquid at a temperature of 100 °C or higher (such as 110 °C or higher, such as 120 °C or higher) and a CO partial pressure of 6.9 MPa or higher, or 10 MPa or higher.

[0129] Preferably, the catalyst system described herein does not decompose at a CO partial pressure of less than 10 MPa.

[0130] Preferably, the catalyst system described herein is stable at a temperature of 80 °C or higher and a CO partial pressure of less than 10 MPa.

[0131] Preferably, the catalyst system described herein is liquid at a temperature of 10 °C or higher and optionally at a CO partial pressure of 6.9 MPa or higher.

[0132] As described above, the dimeric Group 9 metal complex of the present disclosure is an effective precatalyst for in-situ formation of an active catalytic species under hydroformylation reaction conditions. The term "hydroformylation" as used herein refers to a combined process of introducing an aldehyde moiety into an olefin and subsequently reducing the aldehyde moiety to a primary alcohol moiety. To distinguish between the two process operations herein, the initially produced non-reduced (aldehyde) reaction product may be referred to as the "hydroformylation reaction product" in the present disclosure, and the reduced (alcohol) reaction product may be referred to as the "reduced hydroformylation reaction product" herein.

[0133] Accordingly, the hydroformylation method of the present disclosure may include contacting an olefin with syngas and a precatalyst comprising a reaction product of Co2(CO)8 and PF3 under conditions effective to convert the olefin into a hydroformylation reaction product. In a more specific example, the reaction product of Co2(CO)8 and PF3 may have a structure represented by Formula 1, Formula 2, or Formula 3a / 3b, wherein the variables associated with these formulas are as described above. Accordingly, in a more specific example, the hydroformylation method of the present disclosure characterized by in-situ catalyst generation may comprise contacting an olefin with syngas and a precatalyst comprising a compound having Formula 1, wherein M, m, and n are as defined above, and converting the olefin into a hydroformylation reaction product under conditions effective to convert the olefin into a hydroformylation reaction product.

[0134] In the disclosure of the present invention, the conditions for effectively converting an olefin into a hydroformylation reaction product may include a combined hydrogen and carbon monoxide partial pressure of at least about 1,000 psig (6.9 MPa) or at least about 1,500 psig (10 MPa), preferably the conditions include a syngas partial pressure of at least about 1,000 psig (6.9 MPa) or at least about 1,500 psig (10 MPa). The hydroformylation process may further include forming an active hydroformylation catalyst comprising a compound of formula 4 under conditions effective to convert an olefin into a hydroformylation reaction product, wherein M, m′, and n′ are as defined above for formula 4.

[0135] Alternatively, the hydroformylation process of the present invention may include forming an active hydroformylation catalyst of formula 4 under conditions effective to convert an olefin into a hydroformylation reaction product, wherein the variables are as defined above.

[0136] Suitable olefins that can be hydroformylated according to the disclosure herein are represented by formula 5 below.

[0137]

[0138] In formula 5, R 1 、R 2 、R 3 and R 4 can independently be selected from hydrogen or a C1-C 30 linear or branched hydrocarbon group which may be optionally substituted.

[0139] Suitable olefins can be α-olefins or internal olefins, both of which can be linear or branched. In addition, suitable olefins may have one or more carbon-carbon double bonds. One suitable type of olefin feed that can undergo hydroformylation according to the disclosure herein may comprise a mixture of various olefin isomers (such as one or more propylene oligomers). More specifically, such an olefin feed may represent a mixture comprising two or more of α-olefins, ethylidene olefins, vinyl olefins, trisubstituted olefins, tetrasubstituted olefins, or any combination thereof.

[0140] Non-limiting examples of α-olefins that can be hydroformylated according to the disclosure herein include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane, vinylnorbornene, or any combination thereof. Poly-α-olefins containing any one or any combination of these α-olefins (such as their oligomers) may also contain double bonds that can undergo hydroformylation according to the disclosure herein.

[0141] Suitable olefin feeds may also include lower olefins (such as C2-C 30 , such as C3-C 12 ), such as the oligomerization products of propylene, in which a variety of branched olefin products may be present. For example, suitable olefin feeds may contain one or more of C2, C3, or C4 olefin oligomers. The term "oligomer" refers to a molecule having 2 to 100 (such as 2 to 20, such as 3 to 10) repeating monomer units. Schematic oligomers include dimers, trimers, tetramers, pentamers, and hexamers and mixtures thereof. In particular, C2-C 20 olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene oligomers (usually containing 2 to 12 monomer units, such as oligomers of 3, 4, 5, or 6 monomer units) are useful herein. A commercially available olefin feed suitable for the disclosure herein is a composition containing highly branched higher olefins sold by ExxonMobil Chemical Company (Houston, Texas) under the name Tetramer K TM and containing a high concentration of isomeric C 12 olefins.

[0142] An olefinic hydrocarbon can be contacted with the pre-catalyst of the disclosure herein according to Scheme 1 below, in which a branched or unbranched aldehyde can be formed, depending on the regioselectivity achieved by introducing the carbonyl group. Branching already present in the olefinic hydrocarbon can be retained in the hydroformylation process.

[0143]

[0144] Scheme 1

[0145] wherein R 1 、R 2 、R 3 and R 4 is H or a hydrocarbon group, M is a Group 9 metal, m is 1, 2, 3, 4, 5, 6 or 7, and n is 1, 2, 3, 4, 5, 6 or 7.

[0146] The effective amount of the pre-catalyst for hydroformylation disclosed herein can be from about 150 μmol pre-catalyst / mol olefin feed to about 8,000 μmol pre-catalyst / mol olefin feed, or from about 100 ppm metal to about 5,000 ppm metal (where ppm is defined as mg metal / kg olefin feed, preferably where the metal is cobalt). The loading can depend on the complexity of the substrate. For example, lower loadings can be used for lighter α-olefins, while more challenging substrates can employ higher catalyst loadings. In one or more embodiments, the pre-catalyst loading can be about 2,400 μmol pre-catalyst / mol olefin feed or about 1,500 ppm. Under conditions effective to promote hydroformylation, the pre-catalyst can be converted into an active hydroformylation catalyst with at least one PF3 ligand. The in-situ generated active hydroformylation catalyst can then promote the conversion of the olefin to the hydroformylation reaction product. The conditions for effectively converting the olefin to the hydroformylation reaction product can include a syngas pressure of at least about 1,000 psig (about 7 MPa) or at least about 1,500 psig (about 10 MPa). Suitable ranges include from about 1,000 psig (∼7 MPa) to about 2,000 psig (∼13.8 MPa), from about 1,250 psig (∼8.6 MPa) to about 1,500 psig (∼10 MPa), from about 1,500 psig (∼10 MPa) to about 1,750 psig (∼12 MPa), or from about 1,500 psig (∼10 MPa) to about 2,000 psig (∼13.8 MPa). The conditions for effectively converting the olefin can further include a temperature of about 100 °C to about 200 °C, which includes about 125 °C to about 175 °C, about 125 °C to about 200 °C, and about 100 °C to about 175 °C. In an exemplary embodiment, a temperature of about 150 °C can be used to form the active hydroformylation catalyst and conduct the hydroformylation. The reaction time under these conditions can be from about 0.5 hours to about 96 hours. Optionally, additional PF3 can be introduced into the reactor to control the number of PF3 ligands associated with the active hydroformylation catalyst. Both batch and continuous reaction conditions can be used to produce the hydroformylation reaction product according to the disclosure herein. For continuous reaction conditions, any of a continuous stirred tank reactor, a plug flow reactor, or a loop reactor can be used. When conducting the hydroformylation reaction according to the disclosure herein, a solvent or diluent is not required. When used, suitable solvents or diluents can include but are not limited to alkane solvents, polar protic solvents, polar aprotic solvents, chlorinated solvents, and aromatic solvents. In a particular instance, up to about 10 wt% water can be added to control the formation of by-products under the hydroformylation reaction conditions. Without being bound by theory or mechanism, water may impede the formation of aldol condensates and other heavy reaction products.

[0147] The diversity and complexity of the hydroformylation reaction products formed according to the present disclosure can depend on the diversity and complexity of the olefins from which they are formed. Depending on the regiochemical position at which the carbonyl group is introduced, the hydroformylation reaction products can be linear or branched. Any branching already present in the olefin can be retained when undergoing hydroformylation according to the present disclosure. Thus, in any embodiment, the hydroformylation reaction products can comprise a mixture of isomers that differ in size, branching, and aldehyde position (i.e., at the terminal or non-terminal positions of the carbon backbone). Based on their relative formation rates, the hydroformylation reaction products of the present disclosure can comprise a mixture of aldehydes in which each aldehyde molecule exhibits an average of about 1.2 to about 2 branches per aldehyde molecule, and if additional branching is present in the olefin prior to hydroformylation and / or additional branching is introduced during hydroformylation, then the branching can exceed that.

[0148] The conversion selectivity of the olefin feedstock to the hydroformylation reaction products can depend on the complexity of the olefin feedstock. Advantageously, the precatalysts disclosed herein can promote the hydroformylation of α-olefins and have high selectivity for branched aldehydes when compared to other phosphine-modified cobalt complexes. For example, the ratio of linear aldehyde to branched aldehyde can be less than or equal to about 2, such as from about 0.9 to about 2, although ratios below 0.9 can be obtained. Additionally, the precatalysts disclosed herein can convert α-olefins to products at higher conversions than other phosphine-modified cobalt complexes. For example, an olefin feed comprising an α-olefin can be converted to a hydroformylation reaction product comprising from about 85 mol% to about 99 mol%, preferably from about 90 mol% to about 95 mol% aldehyde molecules. In contrast, hydroformylation reaction products produced using an unmodified cobalt complex (i.e., Co(CO)8) can produce a lower percentage of aldehydes and higher amounts of alcohol and / or paraffin by-products.

[0149] In more complex olefin feeds, e.g., an olefin feed comprising various linear and branched olefin isomers, the conversion of the olefin feed to aldehydes, alcohols, and C n+1 paraffins (where n is the average number of carbons per olefin molecule) can be lower, e.g., about 15 mol% to about 25 mol%. This conversion is surprising and significant considering that phosphine-modified ligands typically exhibit poor performance on these types of complex feeds. The percentage of conversion can be calculated according to the following equation in any embodiment of the present disclosure:

[0150]

[0151] In industrial applications, it may be desirable to recover the hydroformylation catalyst for recycle and reuse, which may require separation of the hydroformylation catalyst from the hydroformylation reaction product. Although conventional phosphine ligands impede catalyst volatilization and make catalyst recycle more difficult (e.g., by utilizing complex catalyst recycle loops with multiphase extraction or other expensive methods), the precatalysts disclosed herein provide a route to obtain a phosphine-modified active hydroformylation catalyst and remain suitable for gas-phase catalyst recovery. Accordingly, the methods disclosed herein can further comprise recovering the hydroformylation catalyst or its waste form (e.g., by gas-phase recovery, typically using CO, syngas, hydrogen, or nitrogen as the stripping gas), and conveying the recovered catalyst to an upstream location for reuse. The stripping gas typically entrains Group 9 metal compounds (e.g., volatile Group compounds, such as volatile cobalt compounds) in the stripping gas such that the metal compounds can be removed (e.g., by taking off the top).

[0152] Optionally, by subjecting the hydroformylation reaction product to reducing conditions, e.g., by catalytic hydrogenation of the aldehyde carbonyl, the hydroformylation reaction product can be further converted to a reduced hydroformylation reaction product. Accordingly, some hydroformylation methods of the invention can include providing an olefin feed comprising an olefin, contacting the olefin with a precatalyst comprising a compound having the formula M2(CO) m (PF3) n (wherein M, m, and n are as previously described above) under conditions effective to convert the olefin to a hydroformylation reaction product, and reducing the hydroformylation reaction product to produce a reduced hydroformylation reaction product. In many cases, the reduction can be carried out by catalytic hydrogenation. Suitable hydrogenation catalysts and hydrogenation conditions are familiar to those of ordinary skill in the art. Exemplary hydrogenation conditions and catalysts are provided hereinafter.

[0153] The reduction can include exposing the hydroformylation reaction product to hydrogen and a hydrogenation catalyst (i.e., catalytic hydrogenation conditions using a catalyst comprising Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, or Pt, preferably supported on an inorganic matrix, with a hydrogen partial pressure of, for example, about 5 MPa to about 20 MPa and a reaction temperature up to about 180 °C). Alternatively, a hydride reducing agent, such as sodium borohydride, can be used for the reduction. Catalytic hydrogenation can remove any residual carbon-carbon unsaturation present in the hydroformylation reaction product, as well as reduce at least a portion of the aldehyde groups to primary alcohols. Hydride reduction, carried out alone or in combination with catalytic hydrogenation, can complete the reduction of the aldehyde moiety to the primary alcohol moiety in the reduced hydroformylation reaction product. In an exemplified method configuration, the reduction can comprise exposing the hydroformylation reaction product to catalytic hydrogenation, followed by sodium borohydride reduction to produce a reduced hydroformylation reaction product.

[0154] The diversity and complexity of the reduced hydroformylation reaction products can depend on the diversity and complexity of the hydroformylation reaction products being reduced. Thus, in any embodiment, the reduced hydroformylation reaction products can comprise a mixture of isomers that differ in size, branching, and alcohol position (i.e., at the terminal or non-terminal positions of the carbon backbone). As used herein, the term "carbon backbone" refers to the longest series of covalently bonded carbon atoms that form the continuous chain of the hydrocarbon molecule. Optionally, the reduced hydroformylation reaction products can be further processed, for example by distillation, to separate particularly desired fractions, such as C 13 alcohols. As a non-limiting example, reduced hydroformylation reaction products resulting from the hydroformylation and subsequent reduction of complex olefin feeds can be particularly valuable in the manufacture of detergents.

[0155] Although the trifluorophosphine-modified cobalt complexes disclosed herein can exhibit lower conversion efficiencies when compared to unmodified cobalt carbonyl complexes, it is predicted that the use of the trifluorophosphine-modified cobalt complexes of the present disclosure avoids cobalt plating that would offset such reduced efficiency.

[0156] The present disclosure relates to the following non-limiting embodiments.

[0157] A. A composition comprising a trifluorophosphine-modified metal carbonyl compound. The composition comprises: a compound having the formula:

[0158] M2(CO) m (PF3) n ;

[0159] wherein M is a Group 9 metal, m and n are independently 1, 2, 3, 4, 5, 6, or 7, and the sum of m and n is 8.

[0160] B. A hydroformylation process. The process comprises: contacting an olefin with syngas and a pre-catalyst comprising a reaction product of Co2(CO)8 and PF3 under conditions effective to convert the olefin to a hydroformylation reaction product.

[0161] C. A hydroformylation process using a pre-catalyst. The process comprises: forming an active hydroformylation catalyst having the formula:

[0162] HCo(CO) m′ (PF3) n′

[0163] wherein m' and n' are integers and the sum of m' and n' is 4; and contacting an olefin with the active hydroformylation catalyst and syngas under conditions effective to convert the olefin to a hydroformylation reaction product.

[0164] Embodiments A - C can have any combination of one or more of the following elements:

[0165] Element 1: where M is cobalt.

[0166] Element 2: where m is 2, 3, 4, 5, 6, or 7.

[0167] Element 3: where the compound has two bridging carbon monoxide groups between the first and second metal centers, respectively.

[0168] Element 4: where the compound has a structure represented by the following formula:

[0169]

[0170] where L 1 , L 2 and L 3 in which at least one is CO, L 4 , L 5 and L 6 in which at least one is CO, and any L 1 -L 6 that is not CO is PF3, and there is at least one PF3.

[0171] Element 5: where m and n are each 4.

[0172] Element 6: Two of L 1 , L 2 , L 3 and L 7 are PF3, and one of L 1 , L 2 , L 3 and L 7 is CO, and two of L 4 , L 5 , L 6 and L 8 are PF3, and one of L 4 , L 5 , L 6 and L 8 is CO.

[0173] Element 7: where the compound has a structure represented by one or more of the following formulas:

[0174]

[0175] where, if the compound is carbonyl - bridged, at least one of L 1 -L 6 is PF3 and any L that is not PF31 -L 6 is CO, and if the compound has a cobalt-cobalt bond, then L 1 -L 8 at least one of which is PF3 and any L that is not PF3 1 -L 8 is CO.

[0176] Element 8: wherein the reaction product of Co2(CO)8 and PF3 comprises a compound having the formula:

[0177] Co2(CO) m (PF3) n ;

[0178] wherein m and n are independently 1, 2, 3, 4, 5, 6, or 7, and the sum of m and n is 8.

[0179] Element 9: wherein the method further comprises forming an active hydroformylation catalyst comprising a compound having the formula, from the reaction product, under conditions effective to convert an olefin into a hydroformylation reaction product:

[0180] HCo(CO) m′ (PF3) n′

[0181] wherein m' and n' are independently 1, 2, or 3, and the sum of m' and n' is 4'.

[0182] Element 10: wherein the method further comprises converting the hydroformylation reaction product into a reduced hydroformylation reaction product by hydrogenating the formylation reaction product.

[0183] Element 11: wherein the conditions effective to convert an olefin into a hydroformylation reaction product include a syngas pressure of at least about 1,000 psig (6.9 MPa).

[0184] Element 12: wherein m' is 2 or 3.

[0185] Element 13: wherein m' and n' are each 2.

[0186] Element 14: wherein the olefin comprises an alpha-olefin.

[0187] Element 15: wherein the hydroformylation reaction product is characterized by a ratio of linear aldehyde to branched aldehyde of from about 0.9 to about 2.

[0188] Element 16: wherein the olefin comprises an alpha-olefin, a vinylidene olefin, a vinyl olefin, a trisubstituted olefin, a tetrasubstituted olefin, or any combination thereof.

[0189] Element 17: wherein the olefin comprises one or more propylene oligomers.

[0190] Element 18: wherein an active hydroformylation catalyst is formed from a pre-catalyst under conditions effective to convert the olefin into a hydroformylation reaction product, the pre-catalyst comprising a compound having the formula:

[0191] Co2(CO) m (PF3) n ;

[0192] wherein m and n are independently 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

[0193] Element 19: wherein the conditions effective to convert the olefin into a hydroformylation reaction product include a syngas pressure of at least about 1,000 psig (6.9 MPa).

[0194] Element 20: wherein the method further comprises converting the hydroformylation reaction product into a reduced hydroformylation reaction product by hydrogenating the formylation reaction product.

[0195] Element 21: wherein m′ is 1, 2 or 3.

[0196] Element 22: wherein m′ and n′ are each 2.

[0197] Element 23: wherein the olefin comprises alpha-olefins.

[0198] Element 24: wherein the hydroformylation reaction product is characterized by a ratio of linear aldehyde to branched aldehyde of from about 0.9 to about 2.

[0199] Element 25: wherein the olefin comprises alpha-olefins, ethylidene olefins, vinyl olefins, trisubstituted olefins, tetrasubstituted olefins, or any combination thereof.

[0200] Element 26: wherein the olefin comprises one or more propylene oligomers.

[0201] As non-limiting examples, illustrative combinations applicable to A include, but are not limited to: 1 and 2; 1 - 3; 1 and 3; 1, 4 and 5; 1 and 4 - 6; 1, 2 and 7; 2 and 3; 2 and 4; 2, 4 and 5; 2 and 6; 2 and 7; 3 and 4; 3 - 5; 3 - 6; 3 and 7; 4 and 5; and 4 - 6. Illustrative combinations applicable to B include, but are not limited to: 9 and 10; 9 and 11; 9 and 12; 9 and 13; 9 and 14; 9 and 15; 9 and 16; 9 and 17; 10 and 11; 10 and 12; 10 and 13; 10 and 14; 10 and 15; 10 and 16; 10 and 17; 11 and 12; 11 and 13; 11 and 14; 11 and 15; 11 and 16; and 11 and 17. Illustrative combinations applicable to C include, but are not limited to: 18 and 19; 18 and 20; 18 and 21; 18 and 22; 18 and 23; 18 and 24; 18 and 25; 18 and 26; 19 and 20; 19 and 23; 19 and 24; 19 and 25; 19 and 26; 20 and 23; 20 and 24; 20 and 25; and 20 and 26.

[0202] The present disclosure also relates to:

[0203] 1. A composition comprising a compound having the formula:

[0204] M2(CO) m (PF3) n ;

[0205] wherein M is a Group 9 metal, m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

[0206] 2. The composition of paragraph 1, wherein M is cobalt.

[0207] 3. The composition of paragraph 1 or 2, wherein m is 2, 3, 4, 5, 6 or 7.

[0208] 4. The composition of any one of paragraphs 1 - 3, wherein the compound has two bridging carbon monoxide groups between the first and second metal centers, respectively.

[0209] 5. The composition of any one of paragraphs 1 - 4, wherein the compound is represented by the formula:

[0210]

[0211] wherein L 1 、L 2 、L 3 、L 4 、L 5 and L 6 are independently CO or PF3, provided that L 1 、L2 and L 3 at least one of which is CO, L 4 , L 5 and L 6 at least one of which is CO, and L 1 , L 2 , L 3 , L 4 , L 5 and L 6 at least one of which is PF3.

[0212] 6. A composition according to any one of paragraphs 1 - 4, wherein m and n are each 4.

[0213] 7. The composition of paragraph 5, wherein L 1 , L 2 , L 3 and L 7 at least two of which are PF3, and L 1 , L 2 , L 3 and L 7 at least one of which is CO, and L 4 , L 5 , L 6 and L 8 at least two of which are PF3, and L 4 , L 5 , L 6 and L 8 at least one of which is CO.

[0214] 8. The composition of paragraph 1, wherein the compound is represented by one or more of the following formulas:

[0215]

[0216] wherein L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 and L 8 are independently CO or PF3, and if the compound is carbonyl - bridged, then at least one of L 1 -L 6 is PF3, and any L that is not PF3 1 -L 6 is CO, and if the compound has a cobalt - cobalt bond, then at least one of L 1 -L 8 is PF3, and any L that is not PF3 1 -L8 It is CO.

[0217] 9. The composition of paragraph 1, wherein M is Rh.

[0218] 10. A catalyst system comprising the reaction product of a compound as in any one of paragraphs 1 to 9 above and hydrogen.

[0219] 11. The catalyst system of paragraph 10, wherein the catalyst system does not decompose under a CO partial pressure of less than 10 MPa.

[0220] 12. The catalyst system of paragraph 10, wherein when tested under the same hydroformylation reaction conditions, the catalyst system does not produce a hydroformylation reaction product having more Group 9 metal precipitate per gram compared to that produced per gram by a catalyst system consisting essentially of the reaction product of HCo(CO)4 and hydrogen.

[0221] 13. The catalyst system of paragraph 10, wherein the catalyst system is stable at a temperature of 80 °C or higher and under a CO partial pressure of less than 10 MPa.

[0222] 14. The catalyst system of paragraph 10, wherein the catalyst system is liquid at a temperature of 10 °C or higher and optionally under a CO partial pressure of 6.9 MPa or higher.

[0223] 15. A method comprising contacting an olefin with a catalyst system as in any one of paragraphs 10 to 14 under conditions effective to convert the olefin into a hydroformylation reaction product.

[0224] 16. A method comprising: contacting an olefin with a composition as in any one of paragraphs 1 to 9, hydrogen, and an oxygen source under conditions effective to convert the olefin into a hydroformylation reaction product.

[0225] 17. A method comprising: contacting an olefin with a hydrogen source and a pre-catalyst comprising the reaction product of Co2(CO)8 and PF3 under conditions effective to convert the olefin into a hydroformylation reaction product.

[0226] 18. A method comprising: contacting an olefin with a hydrogen source, an oxygen source, and a pre-catalyst comprising the reaction product of Co2(CO)8 and PF3 under conditions effective to convert the olefin into a hydroformylation reaction product.

[0227] 19. The method according to paragraph 17 or 18, wherein the pre-catalyst is a composition as in any one of paragraphs 1 to 14.

[0228] 20. The method of paragraph 17 or 18, further comprising: forming, under conditions effective to convert an olefin into a hydroformylation reaction product, an active hydroformylation catalyst from the reaction product that comprises a compound represented by the formula HCo(CO) m′ (PF3) n′ wherein m′ is 1, 2, or 3, n′ is 1, 2, or 3, and the sum of m′ and n′ is 4.

[0229] 21. The method of any one of paragraphs 15 to 20, further comprising converting the hydroformylation reaction product into a reduced hydroformylation reaction product by hydrogenating the hydroformylation reaction product.

[0230] 22. The method of any one of paragraphs 15 - 20, wherein the conditions effective to convert an olefin into a hydroformylation reaction product include a combined H and O partial pressure of at least about 6.9 MPa.

[0231] 23. The method of any one of paragraphs 15 - 20, wherein the conditions effective to convert an olefin into a hydroformylation reaction product include a combined H and CO partial pressure of at least about 6.9 MPa.

[0232] 24. The method of any one of paragraphs 20 to 23, wherein m′ is 2 or 3.

[0233] 25. The method of any one of paragraphs 20 to 23, wherein m′ and n′ are each 2.

[0234] 26. The method of any one of paragraphs 15 - 25, wherein the olefin comprises an α-olefin.

[0235] 27. The method of paragraph 26, wherein the hydroformylation reaction product has a linear aldehyde to branched aldehyde ratio of from about 0.9 to about 2.

[0236] 28. The method of any one of paragraphs 15 - 25, wherein the olefin comprises an α-olefin, a vinylidene olefin, a vinyl olefin, a trisubstituted olefin, a tetrasubstituted olefin, or any combination thereof.

[0237] 29. The method of any one of paragraphs 15 - 17, wherein the olefin comprises one or more propylene oligomers.

[0238] 30. A method comprising: forming, under conditions effective to convert an olefin into a hydroformylation reaction product, an active hydroformylation catalyst represented by the formula: HCo(CO) m′ (PF3) n′ ; wherein m′ is 1, 2, or 3, n′ is 1, 2, or 3, and m′ + n′ is 4; and contacting the olefin with the active hydroformylation catalyst and syngas under conditions effective to convert the olefin to a hydroformylation reaction product.

[0239] 31. The method of paragraph 30, wherein the active hydroformylation catalyst is formed from a precatalyst under conditions effective to convert an olefin into the hydroformylation reaction product, the precatalyst comprising a compound represented by the formula:

[0240] Co2(CO) m (PF3) n ;

[0241] wherein m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

[0242] 32. The method of paragraph 30 or paragraph 31, wherein the conditions effective to convert an olefin into the hydroformylation reaction product include a syngas pressure of at least about 6.9 MPa.

[0243] 33. The method of any one of paragraphs 30 to 32, further comprising: converting the hydroformylation reaction product into a reduced hydroformylation reaction product by hydrogenating the hydroformylation reaction product.

[0244] 34. The method of any one of paragraphs 30 to 33, wherein m′ is 1, 2 or 3.

[0245] 35. The method of any one of paragraphs 30 to 33, wherein m′ and n′ are each 2.

[0246] 36. The method of any one of paragraphs 30 - 35, wherein the olefin includes an α-olefin.

[0247] 37. The method of paragraph 36, wherein the hydroformylation reaction product has a ratio of linear aldehyde to branched aldehyde of from about 0.9 to about 2.

[0248] 38. The method of any one of paragraphs 30 to 35, wherein the olefin comprises an α-olefin, a vinylidene olefin, a vinyl olefin, a trisubstituted olefin, a tetrasubstituted olefin, or any combination thereof.

[0249] 39. The method of any one of paragraphs 30 to 35, wherein the olefin comprises one or more propylene oligomers.

[0250] 40. The method of paragraphs 15 to 39, further comprising recovering the hydroformylation catalyst or its waste form and transporting the recovered catalyst to an upstream location for reuse.

[0251] 41. The method of paragraph 40, wherein the hydroformylation catalyst or its waste form is recovered by vapor-phase recovery.

[0252] The method of paragraph 41, wherein the gas phase recycles CO, syngas, hydrogen or nitrogen as the stripping gas.

[0253] To facilitate a better understanding of the embodiments of the present disclosure, examples of the following preferred or representative embodiments are given. The following examples should in no way be construed as limiting or defining the scope of the present disclosure. Examples

[0254] Unless otherwise stated, materials are handled using standard glovebox and Schlenk techniques. All potentially air-sensitive materials are operated under dry nitrogen. Reagent-grade starting materials are purchased from commercial suppliers and used as received or purified according to standard procedures. Anhydrous solvents are purchased from commercial sources and stored on activated molecular sieves following standard procedures for drying and degassing. NMR data are recorded on Bruker 400 MHz and 500 MHz NMR spectrometers. Chemical shifts are reported in ppm relative to SiMe4 ( 13 C{ 1 H} δ = 0.0 ppm). 13 C{ 1 H} chemical shifts are reported relative to H3PO4 at δ = 0.0 ppm. 31 P NMR chemical shifts are reported at δ = 0.0 ppm for H3PO4, and 19 F NMR chemical shifts are reported at δ = -76.55 ppm for trifluoroacetic acid. Attenuated total reflection (ATR) Fourier transform infrared (FTIR) data are recorded on a Bruker Alpha IR instrument using a single bounce diamond ATR crystal.

[0255] The hydroformylation reaction is carried out using a high-pressure C-276 alloy autoclave reactor (250 ml) equipped with supervisory control and data acquisition capabilities. The interior of the reactor is lined with glass. In a typical experiment, the olefin feed (60 mL) is introduced into the reactor through an air-free inlet connected to a feed storage container. Stirring is started and the reactor is brought to the specified process temperature and a syngas pressure 100 psig (690 kPa) lower than the specified process pressure (1:1 v / v H2:CO). The reaction mixture is stirred for 10 minutes to equilibrate. Then, a solution of the specified catalyst (20 mL) is delivered through an injection port on the autoclave. Syngas is used to drive the catalyst injection while bringing the unit to the specified process pressure. The process pressure is maintained with syngas throughout the reaction and metered by a mass flow controller. At the end of the run, the supply of syngas is stopped and the unit is depressurized and purged with nitrogen. Once cooled, the reactor is opened and the liquid hydrocarbon product is transferred to a sample container for offline product analysis.

[0256] Example 1: Preparation and Characterization of a Pre-Catalyst. Co2(CO)8 (10 g, 29.42 mmol) was dissolved in toluene (50 mL). The resulting solution was transferred to a glass-lined autoclave equipped with a magnetic stir bar. The autoclave was then sealed, pressurized with PF3 (150 psig (1 MPa)), and allowed to react at 30 °C for 16 h. Thereafter, the autoclave was depressurized, and the reaction mixture was transferred to a round-bottom flask, where it was placed under reduced pressure (∼200 mTorr (26.6 Pa)) for 5 h to remove residual solvent and other volatile components. A dense red / brown liquid (∼10 mL) was obtained. The reaction product was characterized by ATR-FTIR spectroscopy, and 13 C{ 1 H}NMR, 31 P{ 1 H}NMR, and 19 F NMR spectroscopy.

[0257] Figure 1 The ATR-FTIR spectrum of the reaction product of Example 1 is shown, Figure 2 The ATR-FTIR spectrum of the reaction product of Example 1 is shown, superimposed on the simulated IR spectra of two possible Co2(CO)4(PF3)4 isomers. The ATR-FTIR spectrum of the reaction product shows absorbances at 2085, 2037, and 1831 cm -1 . These peaks are assigned to the stretching of terminal and bridging carbonyls, respectively. The high-intensity stretch at 839 cm -1 is assigned to P-F stretching. No absorbance attributable to residual hydrocarbon solvent is observed at 3,000 or 1,500 cm -1 . The simulated IR spectra ( Figure 2 ) confirm that the experimental IR spectrum is in good correlation with the theoretically expected spectrum. The simulated IR spectra were collected using the Amsterdam Density Functional (ADF) program suite, version 2016.106. ADF was used to perform density functional theory calculations and IR simulations. For all calculations, a triple-ζ Slater-type orbital (TZ2P) ADF basis set without frozen cores was utilized. Relativistic effects were included by using the zero-order regular approximation (ZORA). The local density approximation (LDA) in the exchange and correlation functions is an implementation of ADF from Vosko, Wilk, and Nussair (VWN). The generalized gradient approximation (GGA) employs the BP86 GGA function of ADF using Becke (exchange) and Perdew (correlation). Vibrational frequency calculations (IR simulations) were performed on the molecular structure with geometric optimization having a stable energy minimum. The simulated vibrational spectra were visualized with the ADFView graphical program, and the spectra were output as XY files.

[0258] Figures 3 - 5shows the reaction product of Example 1 19 F, 31 P{ 1 H}, and 13 C{ 1 H} NMR spectra. The NMR spectra are consistent with the presence of these nuclei in a variety of chemical environments. All NMR spectra show broad agreement with the coupling to 59 Co (S = 7 / 2, 100% abundance).

[0259] Example 2: Hydroformylation with 1 - hexene feedstock. 1 - Hexene was used as a model substrate to illustrate the product selectivity differences between hydroformylation using an unmodified cobalt catalyst precursor (Co2(CO)8) compared to the trifluorophosphine - modified cobalt catalyst precursor (Example 1). As a further comparison, a conventional phosphine - modified cobalt catalyst (Co2(CO)8 + 4 equivalents PPh3) was also run under similar hydroformylation conditions. The reaction was carried out at 1,500 psig (10 MPa, 1:1 H2 / CO), 150 °C, and 1,500 ppm cobalt for 1 hour. The reaction products were analyzed by gas chromatography, and the results are summarized in Table 1 below.

[0260] Table 1

[0261]

[0262] Table 1 continued

[0263]

[0264] Notably, the PF3 - modified cobalt catalyst (entry 1) appears to be substantially more active than the cobalt catalyst modified with a conventional phosphine such as PPh3 (entry 3). The activity of the PF3 - modified cobalt catalyst (entry 1) is lower than that obtained with Co2(CO)8 (entry 2), and the product distribution is significantly different. This observation indicates that, contrary to the behavior observed with conventional phosphines, PF3 remains coordinated to cobalt even at elevated pressures and temperatures. Figures 6 - 8 Gas chromatograms of the products obtained from entries 1, 2, and 3 are shown respectively.

[0265] Notably, no evidence of cobalt plating was observed from the run of entry 1, while significant precipitation was present in the run of entry 2, which was observable visually and by light scattering. In the Figure 9A image, significant plating was observed from the run of entry 2, while the Figure 9B image shows limited plating in the run of entry 1.

[0266] Example 3: Hydroformylation of complex feeds. Repeat Example 2, except as modified in Table 2 below, using TETRAMER K (ExxonMobil, produced by oligomerization of propylene on a solid phosphoric acid catalyst and comprising a mixture of linear α-olefins, linear internal olefins, and highly substituted branched internal olefins (e.g., disubstituted, trisubstituted, and tetrasubstituted) C 12 olefinic hydrocarbons.

[0267] Table 2

[0268] Item Catalyst Pressure (psi) Conversion rate (%) <![CDATA[Conversion frequency (h -1 )]]> 5 Example 1 400 3.44％ 2.68 6 Example 1 1500 21.00％ 16.35 7 Example 1 1500 16.16％ 12.58 8 <![CDATA[Co2(CO)8]]> 1500 50.92％ 79.16

[0269] Phosphine-modified cobalt hydroformylation catalysts generally react poorly with complex feeds such as TETRAMER K. In contrast, the PF3-modified cobalt catalyst of Example 1 exhibits good turnover frequencies and good conversions at high syngas pressures (Entries 6 and 7), but not as high as those observed with Co2(CO)8 (Entry 8). At lower reaction pressures (Entry 5), the conversions and turnover frequencies of the PF3-modified cobalt catalyst of Example 1 are much lower. Figure 10 A schematic gas chromatogram of the product obtained from Example 3 is shown.

[0270] All documents described herein are hereby incorporated by reference in order to permit all permissions for such practice, including any priority documents and / or test procedures, provided they are not inconsistent with the present disclosure. From the foregoing general description and specific examples, it will be apparent that while the forms of the present disclosure have been shown and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended to limit the present disclosure thereby. For example, the compositions described herein may be free of any component or composition not explicitly recited or disclosed herein. Any method may lack any step not recited or disclosed herein. Similarly, the term "comprising" is considered synonymous with the term "including". Whenever the conventional term "including" precedes a method, composition, element, or group of elements, it should be understood that we also contemplate the same composition or group of elements preceded by the conventional terms "consisting essentially of", "consisting of", "selected from the group consisting of", or "is", or vice versa.

[0271] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and the like used in the specification and associated claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0272] Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed. In particular, each value range disclosed herein (of the form "about a to about b," or equivalently, "about a to b," or equivalently, "about a - b") is to be understood to set forth every number and range subsumed within the broader value range. Further, unless the patentee has otherwise clearly and unambiguously defined, the terms in the claims have their ordinary and customary meanings. Additionally, the indefinite articles "a" or "an" as used in the claims are defined herein to mean one or more than one of the element introduced.

[0273] One or more illustrative embodiments are presented herein. For clarity, not all features of a physical implementation are described or shown in this application. It is to be understood that in developing a physical embodiment of the present disclosure, numerous implementation-specific decisions must be made to achieve the developer's goals, such as compliance with system-related, business-related, government-related, and other constraints, which vary by implementation and change over time. While the developer's efforts may be time-consuming, such efforts will be routine tasks for those of ordinary skill in the art and will be benefited by the present disclosure.

[0274] Accordingly, the present disclosure is well-suited to attaining the advantages mentioned as well as those inherent therein. The specific embodiments disclosed above are merely illustrative, as the present disclosure may be modified and practiced in different but equivalent manners that are apparent to those of ordinary skill in the art and that are benefited by the teachings herein. Further, it is not intended to limit the details of construction or design shown herein other than as described in the following claims. Accordingly, it is evident that the specific illustrative embodiments disclosed above may be altered, combined, or modified, and all such variations are considered to be within the scope and spirit of the present disclosure. The embodiments disclosed herein may be practiced appropriately without any element and / or any optional element disclosed herein not specifically disclosed.

Claims

1. A process for converting an olefin into a hydroformylation reaction product, which comprises: Under conditions effective to convert an olefin into a hydroformylation reaction product, contacting the olefin with a composition, hydrogen, and an oxygen source, wherein the composition comprises a compound having the formula: M2(CO) m (PF3) n ; wherein M is cobalt or Rh, m is 1, 2, 3, 4, 5, 6, or 7, n is 1, 2, 3, 4, 5, 6, or 7, and the sum of m and n is 8.

2. The method according to claim 1, wherein M is cobalt.

3. The method according to claim 1, wherein m is 2, 3, 4, 5, 6, or 7.

4. The method according to claim 1, wherein the compound has two bridging carbon monoxide groups each between a first metal center and a second metal center.

5. The method according to claim 1, wherein the compound is represented by the formula: wherein L 1 、L 2 、L 3 、L 4 、L 5 and L 6 are independently CO or PF3, provided that at least one of L 1 、L 2 and L 3 is CO, at least one of L 4 、L 5 and L 6 is CO, and at least one of L 1 、L 2 、L 3 、L 4 、L 5 and L 6 is PF3.

6. The method according to claim 1, wherein m and n are each 4.

7. The method according to claim 5, wherein L 1 , L 2 and L 3 at least two of which are PF3 and L 1 , L 2 and L 3 at least one of which is CO, and L 4 , L 5 and L 6 at least two of which are PF3 and L 4 , L 5 and L 6 at least one of which is CO.

8. The method according to claim 1, wherein the compound is represented by one or more of the formulas: wherein L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 and L 8 are independently CO or PF3, and if the compound is carbonyl-bridged, then at least one of L 1 -L 6 is PF3, and any L 1 -L 6 that is not PF3 is CO, and if the compound has a cobalt-cobalt bond, then at least one of L 1 -L 8 is PF3 and any L 1 -L 8 that is not PF3 is CO.

9. The method according to claim 1, wherein M is Rh.

10. The method according to claim 1, further comprising converting the hydroformylation reaction product into a reduced hydroformylation reaction product by hydrogenating the hydroformylation reaction product.

11. The method according to claim 1, wherein the conditions effective to convert the olefin into the hydroformylation reaction product comprise a combined H and CO partial pressure of at least 6.9 MPa.

12. The method according to claim 1, wherein the olefin comprises an α-olefin.

13. The method according to claim 1, wherein the olefin comprises an α-olefin, a vinylidene olefin, a vinyl olefin, a trisubstituted olefin, a tetrasubstituted olefin, or any combination thereof.

14. The method according to claim 1, wherein the olefin comprises one or more propylene oligomers.

15. A process for converting an olefin into a hydroformylation reaction product, which comprises: Under conditions effective to convert an olefin into a hydroformylation reaction product, contacting the olefin with a hydrogen source and a pre-catalyst that is a reaction product comprising Co2(CO)8 and PF3.

16. The method according to claim 15, further comprising converting the hydroformylation reaction product into a reduced hydroformylation reaction product by hydrogenating the hydroformylation reaction product.

17. The method according to claim 15, wherein the conditions effective to convert the olefin into the hydroformylation reaction product comprise a combined H and CO partial pressure of at least 6.9 MPa.

18. The method according to claim 15, wherein the olefin comprises an α-olefin.

19. The method according to claim 15, wherein the olefin comprises an α-olefin, a vinylidene olefin, a vinyl olefin, a trisubstituted olefin, a tetrasubstituted olefin, or any combination thereof.

20. The method according to claim 15, wherein the olefin comprises one or more propylene oligomers.

21. The method according to claim 15, wherein the pre-catalyst is a composition, wherein the composition comprises a compound having the formula: M2(CO) m (PF3) n ; wherein M is cobalt, m is 1, 2, 3, 4, 5, 6, or 7, n is 1, 2, 3, 4, 5, 6, or 7, and the sum of m and n is 8.

22. The method according to claim 21, wherein m is 2, 3, 4, 5, 6 or 7.

23. The method according to claim 21, wherein the compound has two bridging carbon monoxide groups each between a first metal center and a second metal center.

24. The method according to claim 21, wherein the compound is represented by the following formula: wherein L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are independently CO or PF3, provided that at least one of L 1 , L 2 and L 3 is CO, at least one of L 4 , L 5 and L 6 is CO, and at least one of L 1 , L 2 , L 3 , L 4 , L 5 and L 6 is PF3.

25. The method according to claim 21, wherein m and n are each 4.

26. The method according to claim 24, wherein L 1 、L 2 and L 3 at least two of which are PF3 and L 1 、L 2 and L 3 at least one of which is CO, and L 4 、L 5 and L 6 at least two of which are PF3 and L 4 、L 5 and L 6 at least one of which is CO.

27. The method according to claim 21, wherein the compound is represented by one or more of the following formulas: wherein L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 and L 8 are independently CO or PF3, and if the compound is carbonyl-bridged, then at least one of L 1 -L 6 is PF3, and any L 1 -L 6 that is not PF3 is CO, and if the compound has a cobalt-cobalt bond, then at least one of L 1 -L 8 is PF3 and any L 1 -L 8 that is not PF3 is CO.

28. The method according to claim 15, further comprising: Under conditions effective for converting olefins to hydroformylation reaction products, the reaction product forms an active hydroformylation catalyst comprising a compound represented by the formula HCo(CO) m′ (PF3) n′ wherein m′ is 1, 2 or 3, n′ is 1, 2 or 3, and the sum of m′ and n′ is 4.

29. The method according to claim 28, wherein m' is 2 or 3.

30. The method according to claim 28, wherein m' and n' are each 2.

31. A method for converting an olefin into a hydroformylation reaction product, comprising: Contacting the olefin with a hydrogen source, an oxygen source, and a pre-catalyst of a reaction product comprising Co2(CO)8 and PF3 under conditions effective to convert the olefin into a hydroformylation reaction product.

32. The method according to claim 31, wherein the pre-catalyst is a composition, and the composition comprises a compound having the following formula: M2(CO) m (PF3) n ; wherein M is cobalt, m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

33. The method according to claim 32, wherein m is 2, 3, 4, 5, 6 or 7.

34. The method according to claim 32, wherein the compound has two bridging carbon monoxide groups each between a first metal center and a second metal center.

35. The method according to claim 32, wherein the compound is represented by the following formula: wherein L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are independently CO or PF3, provided that at least one of L 1 , L 2 and L 3 is CO, at least one of L 4 , L 5 and L 6 is CO, and at least one of L 1 , L 2 , L 3 , L 4 , L 5 and L 6 is PF3.

36. The method according to claim 32, wherein m and n are each 4.

37. The method according to claim 35, wherein L 1 , L 2 and L 3 at least two of which are PF3 and L 1 , L 2 and L 3 at least one of which is CO, and L 4 , L 5 and L 6 at least two of which are PF3 and L 4 , L 5 and L 6 at least one of which is CO.

38. The method according to claim 32, wherein the compound is represented by one or more of the following formulas: wherein L 1 、L 2 、L 3 、L 4 、L 5 、L 6 、L 7 and L 8 are independently CO or PF3, and if the compound is carbonyl-bridged, then at least one of L 1 -L 6 is PF3, and any L 1 -L 6 that is not PF3 is CO, and if the compound has a cobalt-cobalt bond, then at least one of L 1 -L 8 is PF3 and any L 1 -L 8 that is not PF3 is CO.

39. The method according to claim 31, further comprising: Under conditions effective to convert an olefin into a hydroformylation reaction product, there is formed from the reaction product an active hydroformylation catalyst comprising a compound represented by the formula HCo(CO) m′ (PF3) n′ wherein m′ is 1, 2 or 3, n′ is 1, 2 or 3, and the sum of m′ and n′ is 4.

40. The method according to claim 31, further comprising converting the hydroformylation reaction product into a reduced hydroformylation reaction product by hydrogenating the hydroformylation reaction product.

41. The method according to claim 31, wherein the conditions effective to convert the olefin into a hydroformylation reaction product comprise a combined H and CO partial pressure of at least 6.9 MPa.

42. The method according to claim 39, wherein m' is 2 or 3.

43. The method according to claim 39, wherein m' and n' are each 2.

44. The method according to claim 31, wherein the olefin comprises an α-olefin.

45. The method according to claim 43, wherein the hydroformylation reaction product has a ratio of linear aldehyde to branched aldehyde of 0.9 to 2.

46. The method according to claim 31, wherein the olefin comprises an α-olefin, a vinylidene olefin, a vinyl olefin, a trisubstituted olefin, a tetrasubstituted olefin, or any combination thereof.

47. A process for converting an olefin into a hydroformylation reaction product, which comprises: An active hydroformylation catalyst represented by the following formula is formed under conditions effective to convert an olefin into a hydroformylation reaction product: HCo(CO) m′ (PF3) n′ ; where m′ is 1, 2, or 3, n′ is 1, 2, or 3, and m′ + n′ is 4; and the olefin is contacted with the active hydroformylation catalyst and syngas under conditions effective to convert the olefin into a hydroformylation reaction product. An active hydroformylation catalyst is formed from a precatalyst under conditions effective to convert an olefin into a hydroformylation reaction product, the precatalyst comprising a compound represented by the following formula: Co2(CO) m (PF3) n ; wherein m is 1, 2, 3, 4, 5, 6 or 7, n is 1, 2, 3, 4, 5, 6 or 7, and the sum of m and n is 8.

48. The method according to claim 47, wherein the conditions effective to convert an olefin into a hydroformylation reaction product comprise a syngas pressure of at least 6.9 MPa.

49. The method according to claim 47, further comprising: The hydroformylation reaction product is converted into a reduced hydroformylation reaction product by hydrogenating the hydroformylation reaction product.

50. The method according to claim 47, wherein m′ is 1, 2 or 3.

51. The method according to claim 47, wherein m′ and n′ are each 2.

52. The method according to claim 47, wherein the olefin comprises an α-olefin.

53. The method according to claim 52, wherein the hydroformylation reaction product has a ratio of linear aldehyde to branched aldehyde of 0.9 to 2.

54. The method according to claim 47, wherein the olefin comprises an α-olefin, a vinylidene olefin, a vinyl olefin, a trisubstituted olefin, a tetrasubstituted olefin, or any combination thereof.

55. The method according to claim 47, wherein the olefin comprises one or more propylene oligomers.

56. The method according to claim 47, further comprising recovering the hydroformylation catalyst or a waste form thereof and transporting the recovered catalyst to an upstream location for reuse.

57. The method according to claim 56, wherein the hydroformylation catalyst or a waste form thereof is recovered by vapor-phase recovery.

58. The method according to claim 57, wherein the vapor-phase recovery uses CO, syngas, hydrogen or nitrogen as a stripping gas.

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