Alkane-Alkene Coupling Via Tandem Alkane-Dehydrogenation/Alkene-Dimerization Catalyzed by Pincer Iridium Catalyst Heterogenized on Solid Supports

Abstract

Disclosed herein are processes for tandem alkene dehydrogenation/alkene dimerization using an iridium pincer complex catalyst on a support comprising magnesium silicates (e.g., Florisil). The reaction process comprises providing an iridium pincer complex bound to a solid support comprising magnesium silicates; providing a gaseous alkane feedstock comprising at least one alkane; and contacting the gaseous alkane feedstock with the iridium pincer complex bound to the solid support in the presence of a hydrogen acceptor to form dimerized alkenes. The processes disclosed herein can accomplish facile, low-temperature tandem transfer dehydrogenation of alkanes and dimerization of alkenes with unprecedented TONs at a reasonable rate of conversion.

Claims

1. A process for preparing dimerized alkenes in a tandem dehydrogenation/alkene dimerization reaction comprising: providing an iridium pincer complex bound to a solid support comprising magnesium silicates; providing a gaseous alkane feedstock comprising at least one alkane; contacting the gaseous alkane feedstock with the iridium pincer complex bound to the solid support in the presence of a hydrogen acceptor to form the dimerized alkenes; and recovering the dimerized alkenes as recovered dimerized alkenes.

2. The process of claim 1, wherein the at least one alkane of the gaseous alkane feedstock comprises 4 or 5 carbons.

3. The process of claim 1, wherein the recovered dimerized alkenes comprise C.sub.7+ dimerized alkenes.

4. The process of claim 3, wherein the recovered dimerized alkenes comprise C.sub.7-19 dimerized alkenes.

5. The process of claim 1, wherein the hydrogen acceptor comprises ethylene, propene or mixtures thereof.

6. The process of claim 1, wherein the iridium pincer complex is (p-OM-.sup.iPr4PCP)Ir(C.sub.2H.sub.4) bound to the solid support comprising magnesium silicate, where M is K or the solid support.

7. The process of claim 1, wherein the process has a TON for C.sub.7+ products of at least 100 at 10 minutes.

8. The process of claim 1, wherein the process has a TON for C.sub.7+ products of at least 185 at 40 minutes.

9. The process of claim 1, wherein the process is run for four cycles with a same iridium pincer complex bound to the solid support.

10. The process of claim 9, wherein the process has a TON for olefins in a fourth cycle of at least 40 at 10 minutes.

11. The process of claim 9, wherein the process has turnover frequency rates (TOF) of at least 4260, 960, 300, and 240 TOh.sup.1 in a first, a second, a third, and the fourth cycle respectively.

12. The process of claim 1, wherein the process has a TON for C.sub.8 of at least 65 after 10 minutes and of at least 125 after 40 minutes.

13. The process of claim 1, wherein the iridium pincer complex has a Formula ##STR00008## wherein M is K or the solid support; n is an integer from 0 to 4; and each L is independently H, alkyl, or alkene.

14. The process of claim 13, wherein L is ethylene.

15. The process of claim 1, wherein the iridium pincer complex is selected from the group consisting of: ##STR00009## ##STR00010## ##STR00011## and mixtures thereof.

16. The process of claim 1, wherein the iridium pincer complex is (p-OM-.sup.iPr4PCP)Ir(C.sub.2H.sub.4) or (p-OM-.sup.iPr4PCP)Ir(C.sub.3H.sub.6), where M is K or the solid support.

17. The process of claim 1, wherein the contacting is performed at a reaction temperature of less than 300 C.

18. The process of claim 17, wherein the reaction temperature is 160 C.-260 C.

19. The process of claim 1, wherein the contacting is performed for up to 24 hours.

20. The process of claim 1, wherein the contacting is performed for 10-100 minutes.

21. An iridium pincer complex of a formula (p-OK-.sup.iPr4PCP)Ir(C.sub.2H.sub.4)

22. The iridium pincer complex of claim 21, wherein the iridium pincer complex is unsupported.

23. The iridium pincer complex of claim 21, wherein the iridium pincer complex is immobilized on a solid support.

24. The iridium pincer complex of claim 23, wherein the solid support comprises magnesium silicate.

Description

DETAILED DESCRIPTION

[0013] Provided are processes for the tandem dehydrogenation of an alkane and dimerization of the produced alkene using an iridium pincer complex. The reaction is in the gas phase and the solid iridium pincer complex is heterogenized on magnesium silicates solid support (for example, MgO.SiO.sub.2 such as Florisil). The process allows an efficient upgrade of low molecular alkanes to fuel grade medium weight (C.sub.7+) hydrocarbons.

[0014] The present process for producing dimerized alkenes comprises providing an iridium pincer complex bound to a solid support comprising magnesium silicates; providing a gaseous alkane feedstock comprising at least one alkane; and contacting the gaseous alkane feedstock with the iridium pincer complex bound to the solid support in the presence of a hydrogen acceptor to form dimerized alkenes. In one embodiment the support is magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil) and the dimerized alkene products in the C.sub.7+ range are recovered. In one embodiment the process further comprises recovering the dimerized alkenes.

[0015] In the dehydrogenation reactions, hydrogen that is co-formed during the process is removed for the chemical reaction to proceed and to prevent the excess hydrogen from poisoning the catalyst. The hydrogen is removed by using an olefin hydrogen acceptor, for example, ethylene or propene.

[0016] The present processes are conducted at lower reaction temperatures and exhibit unprecedented high turnover numbers (TONs). The present processes can show as high as 700 TON or greater at 10 minutes (based on iridium catalyst) and a turnover frequency (TOF) of 4250 TOh.sup.1 or greater for olefin production. More importantly, it has been surprisingly found that the present process offers a TON of at least 100 at 10 minutes for C.sub.7+ products, and at least 185 at 40 minutes. For C.sub.7 products, the TON at 10 minutes can be at least 35, and for dimerized C.sub.8 products the TON at 10 minutes can be at least 65, with the formation of each being at a rate of 210 and 390 TOh.sup.1 respectively. After 40 minutes, the TON for C.sub.8 dimer products can be at least 125.

[0017] It has also been found that the present process shows good recyclability of the catalyst, which is a great economic benefit. The catalyst remains active for up to four cycles. In the fourth cycle, the present processes can have a TON of at least 40 at 10 minutes

[0018] The dehydrogenation reaction is conducted in a closed system and the hydrogen produced reacts with a hydrogen acceptor molecule. The hydrogen acceptors can be ethylene, propene, benzene, and the like, or mixtures thereof. In certain hydrogen acceptor embodiments, the hydrogen acceptors utilized are selected from the group consisting of ethylene, propene, and mixtures thereof. Ethylene, propene, and mixtures thereof are highly abundant light alkenes, readily recyclable, and inexpensive. Propene and ethylene are obtained in abundance as a by-product of oil refining and natural gas processing.

[0019] As such, provided are processes utilizing a hydrogen acceptor selected from the group consisting of ethylene, propene, and mixtures thereof. These hydrogen acceptors can be coordinated with the metal center of the iridium pincer complex. The processes using a hydrogen acceptor comprise utilizing ethylene or propene with an iridium pincer complex on a solid support to dehydrogenate an alkane feedstock, and then surprisingly dimerize the alkene product at a reasonable rate. The combination of the dehydrogenation and dimerization provides the tandem nature of the disclosed process.

[0020] The alkanes to be dehydrogenated can be C.sub.1-C.sub.5 alkanes, which are then upgraded in the present tandem dehydrogenation/dimerization process. The use of iridium pincer complex catalysts disclosed herein has been found to give unprecedented TONs for alkane dehydrogenation and dimerization in the gas phase when the catalyst is bound to magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil) as a support. In some embodiments neutral alumina has also been found to be a good support for the iridium pincer catalyst. The present processes can show a rate of 700 TON or greater at 10 minutes (based on iridium catalyst) and a turnover frequency (TOF) of 4200 TOh.sup.1 or greater.

[0021] Among other factors, it has been discovered that the transfer dehydrogenation of alkanes, such as highly abundant light alkanes like butane and pentane, can be accomplished in the gas phase using readily recyclable and cheap hydrogen acceptors with unprecedented turnover numbers (TONs) and conversion rates. The hydrogen acceptors are alkenes such as propene and ethylene. It has also been discovered that, by reaction in the gas phase with the iridium pincer catalyst heterogenized on magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil) unprecedented tandem dimerization of the alkenes formed occur. The dimerization reaction also occurs with unprecedented TON and turnover rate. This allows for C.sub.7+ valuable fuel grade hydrocarbons to be recovered. In some embodiments the dimerized alkenes are C.sub.7-19.

[0022] As used herein, the term TON (turnover number) refers to the alkenes produced by a mole of iridium pincer complex before it is inactivated or, alternatively, the hydrogen acceptor consumed by a mole of iridium pincer complex before it is inactivated. Increased TONs are associated with increased conversion. For example, the present processes can show a rate of 700 TON or greater at 10 minutes (based on iridium catalyst) and a turnover frequency (TOF) of 4000 TOh.sup.1 (turnovers per hour) or greater. The term TOh.sup.1 (turnovers per hour) means how many feed molecules each catalyst molecule converts per hour. This is a measure of catalytic reaction rate, normalized to the amount of catalyst. For the dimerized products, a TON of at least 100 at 10 minutes and at least 185 at 40 minutes can be realized. For C.sub.7 products, the TON at 10 minutes can be at least 35 and for C.sub.8 products at least 65, with the formation rate of each being 210 and 390 TOh.sup.1 respectively.

Iridium Pincer Complex

[0023] As used herein, the term iridium pincer complex refers to a complex having a tridentate ligand that is connected to iridium via at least one metal-carbon sigma bond with substituents ortho to this sigma bond being held in a fixed position and coordinating to iridium.

[0024] In certain embodiment, the iridium pincer complex can have the following Formula I:

##STR00001##

[0025] wherein the unspecified optionally fused ring system can be any CH construction including optional O and N heteroatoms, including non-fused systems and fused ring systems such as naphthalenes; n is an integer from 0 to 4 and each L is independently H, alkyl, or alkene;

[0026] each R.sub.1 is independently alkyl; and each X is independently O or CH.sub.n, where n=0, 1 or 2.

[0027] In certain embodiments, the iridium pincer complex can have the following Formula (Ia):

##STR00002##

[0028] wherein:

[0029] n is an integer from 0 to 4 and each L is independently H, alkyl, or alkene;

[0030] each R.sub.1 is independently alkyl;

[0031] each X is independently O or CH.sub.2; and

[0032] Y is H or OM wherein M is alkyl, potassium (K), or solid support. When M is a solid support, the iridium pincer complex is bound to the solid support through a functional group.

[0033] In certain embodiments, the iridium pincer complex can have the following Formula (Ib):

##STR00003##

wherein:
n is an integer from 0 to 4 and each L is independently H or alkyl;
each R.sub.1 is independently alkyl;
each X is independently O or CH.sub.2; and
Y is H or OM wherein M is alkyl, K, or solid support.

[0034] In certain embodiments, the iridium pincer complex can have the following Formula

##STR00004##

wherein M is potassium (K) or solid support; n is an integer from 0 to 4; and each L is independently H, alkyl, or alkene.

[0035] In certain embodiments, the iridium pincer complex can be (p-OM-.sup.iPr4PCP)Ir(C.sub.2H.sub.4) or (p-OM-.sup.iPr4PCP)Ir(C.sub.3H.sub.6), wherein M is K or a solid support. When M is a solid support, the iridium pincer complex is bound to the solid support through a functional group.

[0036] As used herein, in connection with the above Formulae, the term alkyl means a branched or straight chain, saturated hydrocarbon radical having 1 to 10 carbons. Exemplary alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and the like. In certain embodiments, the alkyl has 1 to 5 carbons. In other embodiments, the alkyl has 1 to 4 carbons.

[0037] As used herein, in connection with the above Formulae for the iridium pincer complex, the term alkene means a branched or straight chain, unsaturated hydrocarbon having 2 to 5 carbons and one carbon-carbon double bond. Exemplary alkene groups include ethylene, propene, but-1-ene, but-2-ene, and 2-methylpropene. In certain embodiments, the alkene has 2 or 3 carbons. In these embodiments, the alkene is ethylene or propene.

[0038] The iridium pincer complex can be as described in U.S. Pat. No. 6,982,305 to Nagy, which is incorporated herein by reference in its entirety.

[0039] In certain embodiments the iridium pincer complex can also be selected from the group consisting of:

##STR00005## ##STR00006## ##STR00007##

and mixtures thereof.

[0040] The iridium pincer complexes are immobilized on a solid support. When supported on a solid support, the iridium pincer complex is anchored via a covalent bond. The iridium pincer complexes, for the purposes of the present application, are heterogenized on magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil). It is noted that Florisil is available from Sigma-Aldrich. In other embodiments, the solid support can be, for example, neutral alumina. In one embodiment, the pincer complexes have an anchoring group such as OMe (i.e., OCH.sub.3) or OK, which help bond the catalyst to the support.

[0041] In one embodiment of the present processes, the iridium pincer complex utilized is Complex 13 (p-OK-.sup.iPr4PCP)Ir(C.sub.2H.sub.4). Complex 13 is immobilized on a solid support. The solid support can be magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil) or neutral alumina. In one embodiment for purposes of preparing and recovering dimers, Complex 13 (p-OK-.sup.iPr4PCP)Ir(C.sub.2H.sub.4) is immobilized on magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil).

[0042] When the iridium pincer complex is immobilized on a solid support and used in a gaseous reaction, it can exhibit unexpected advantages in the tandem dehydrogenation dimerization process disclosed herein. In one embodiment, the iridium pincer complex immobilized on a solid support can dehydrogenate an alkane to produce an alkene and dimerize the alkene in the presence of a hydrogen acceptor such as ethylene or propene with unprecedented conversion rates and TONs. The supported iridium pincer complex can also exhibit better activity and recyclability in the process disclosed herein than an unsupported complex.

[0043] It has been discovered that the iridium pincer complex of the present processes immobilized on a solid support of magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil) can catalyze the tandem reactions of dehydrogenation and alkane dimerization at lower temperatures (160 C.-260 C.) with unprecedented TONs and conversion rates.

Alkane Feedstock

[0044] The alkane feedstock is gaseous and comprises at least one alkane. As used herein, the term alkane refers to a branched or straight chain, saturated hydrocarbon having from 1-5 carbons, more preferably from 4-5 carbons. Exemplary alkanes include n-butane, isobutane, n-pentane, isopentane, and neopentane. The alkane can be, for example, a butane (e.g. all isomers of butane, including, for example, n-butane, 2-methylpropane, and the like), or a pentane (e.g. all isomers of pentane, including, for example, n-pentane, 2-methylbutane, and the like). In an embodiment, the alkane comprises a butane. In another embodiment, the alkane comprises a pentane. In certain embodiments, the alkane is a straight chain alkane.

[0045] The alkane feedstock can comprise a single alkane or a mixture of alkanes. As such, the alkane to be dehydrogenated can be a single alkane or a mixture of alkanes. The alkane can be a mixture of isomers of an alkane of a single carbon number. The alkane feedstock can comprise hydrocarbons in addition to the alkane or mixture of alkanes to be dehydrogenated. A hydrocarbon feed composition from any suitable source can be used as the alkane feedstock.

[0046] Alternatively, the alkane feedstock can be isolated from a hydrocarbon feed composition in accordance with known techniques such as fractional distillation, cracking, reforming, dehydrogenation, etc. (including combinations thereof). For example, n-paraffin as a feed can be obtained by either by adsorption or extractive crystallization. One suitable source of the alkane feedstock described further herein, by no means to be taken as limiting, is the output of a Fischer-Tropsch reaction system.

[0047] The production of hydrocarbon compositions comprising alkanes from synthesis gas by Fischer-Tropsch catalysis is well known and can be carried out in accordance with known techniques by reaction of a synthesis gas in the presence of Fischer-Tropsch catalyst in a reactor. Any suitable catalyst can be used, including but not limited to iron and cobalt catalysts. See, e.g., U.S. Pat. No. 6,217,830 to Roberts and Kilpatrick; see also U.S. Pat. Nos. 6,880,635; 6,838,487; 6,201,030; 6,068,760; 5,821,270; 5,817,701; 5,811,363; 5,620,676; and 2,620,347.

[0048] The production of synthesis gas from carbonaceous or organic materials, such as coal (including coal fines), natural gas, methane, refinery bottoms, vegetative materials such as wood or other biomass, and combinations thereof, is well known and can be carried out in accordance with known techniques. In some embodiments such production involves the partial oxidation of the carbonaceous or organic material at elevated temperatures, and optionally elevated pressures, with a limited volume of oxygen. The reaction is preferably carried out in a reactor into which the material is fed, together with additional agents such as steam, carbon dioxide, or various other materials. See e.g., U.S. Pat. No. 4,959,080; see also U.S. Pat. No. 4,805,561.

Dimerized Alkene Product

[0049] The gaseous alkane feedstock is dehydrogenated to form an alkene product. The alkene product is then dimerized to form dimerized alkenes. The alkene product comprises at least one alkene. As used herein, in connection with the alkene product, the term alkene refers to a branched or straight chain, unsaturated hydrocarbon having 4 to 8 carbons and one or more carbon-carbon double bonds. The alkene product is dimerized to form dimerized alkenes. The reaction is a tandem reaction and as such, the dehydrogenation is directly followed by dimerization without isolation of an intermediate product. In one embodiment the dimerized alkene product are C.sub.7+ and in certain embodiments are C.sub.7-19.

[0050] The alkene product can contain an alkene with one double bond, a diene (i.e., an alkene with two carbon-carbon double bonds), a dimer, and mixtures thereof. The present process provides the dimers in unprecedented conversion rates and TON.

Reaction Conditions

[0051] In general, the dehydrogenation/dimerization reaction can be run under conventional dehydrogenation reaction conditions. However, the iridium pincer complexes disclosed herein do not require high temperatures or pressures. Therefore, the reaction can be run at a reaction temperature less than 300 C. Higher temperatures up to 400 C. or 500 C. or higher can be used, but are not necessary and are not desired. Suitable temperatures include, for example, a temperature in the range of 160 C.-260 C. In certain embodiments a temperature in the range of 200 C.-260 C. can be utilized. In other embodiments, a temperature in the range of 225 C.-250 C. can be utilized. In yet other embodiments a temperature in the range of 240 C.-250 C. can be utilized. In an embodiment, a temperature of about 240 C. is used, which temperature is sufficient to maintain ethylene or propylene in the gaseous phase. In another embodiment, a temperature of about 200 C. is used. In yet another embodiment, a temperature of about 160 C. is used. The pressure is adjusted accordingly.

[0052] Conducting the dehydrogenation reaction at temperatures of less than 300 C. (e.g., 160 C.-260 C.) results in extremely little to no cracking of the alkane feedstock. Accordingly, the present dehydrogenation reactions can be run with unprecedented selectivities.

[0053] The length of reaction time with best results for selectivity varies based upon the catalyst. The reaction time is generally in the range of from about 1 minute or less (e.g., about 30 seconds) up to 24 hours. The reaction time can be up to about 10 minutes, up to about 40 minutes, up to about 80 minutes, up to about 100 minutes, up to about 180 minutes, or up to about 600 minutes. The reaction time can be about 10 minutes, about 40 minutes, about 80 minutes, about 100 minutes, about 180 minutes, or about 600 minutes. In one embodiment, the reaction time is from about 10-100 minutes. Alternatively, the reaction time can be from about 10-180 minutes. In another embodiment, the reaction time can be from about 20-180 minutes. In another embodiment, the reaction time can be from about 40-100 minutes. In yet another embodiment, the reaction time can be from about 40-180 minutes. The reaction time can be from about 10-40 minutes, about 10-80 minutes, about 10-100 minutes, about 10-180 minutes, or about 10-600 minutes.

[0054] The reaction takes place in the presence of a solid catalyst and a gaseous hydrogen acceptor and a gaseous alkane. The use of a solid catalyst has been found to work well with a gaseous phase for the alkane and for the hydrogen acceptor. In particular, the use of a solid iridium pincer catalyst heterogenized on magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil) has been found to work surprisingly well in the processes as disclosed herein.

[0055] As used herein, the term gas phase refers to the alkane and the hydrogen acceptor both being gaseous during the dehydrogenation reaction. However, during the gas phase reaction, the catalyst is solid. In an embodiment, the reaction is conducted under supercritical conditions.

[0056] The following examples are provided to better illustrate the process disclosed herein. The examples are meant to be solely illustrative, and not limiting.

Example 1

[0057] In a typical supported heterogeneous gas-phase dehydrogenation experimental set-up, the catalyst (p-OK-.sup.iPr4PCP)Ir(C.sub.2H.sub.4) in sealable ampoule was solubilized in a 100 l solvent to give a 1 mM solution and 10 mg of the solid support was added to solution with stirring. The color of the solution gradually disappears and the solid support acquires this color indicating heterogenization of the catalyst. Solvent was then removed under vacuum to yield a free flow supported catalyst. The vials were then sealed under 6 atm of a butane/propene (1:1) gas mixture. One should note that contrary to unsupported heterogeneous systems, coating of the catalyst on walls is not feasible in these supported heterogeneous systems. Hence to attain better activity, the ampoules containing pentane and the supported catalysts were spun in an oven at 200 C. for a stipulated time. The vials were then cooled and the contents analyzed.

TABLE-US-00001 TABLE 1 (p-OK-.sup.iPr4PCP)Ir(C.sub.2H.sub.4) catalyzed gas phase dehydrogenation of n-butane [6.1] with propene [6.1M] as acceptor at 200 C. on various solid supports. Solid Total Olefin Butadiene 1-Butene C.sub.7 C.sub.8 Support Time TON TON TON TON TON 2 mg 10 710 150 80 35 65 Florisil/ 40 1130 250 100 60 125 MgOSiO.sub.2 2 mg 10 130 30 10 5 10 Neutral 40 315 45 20 15 15 Al.sub.2O.sub.3 2 mg 10 75 15 15 2 2 Silica 40 310 60 40 18 35 SiO.sub.2

[0058] Table 1 summarizes the (p-OK-.sup.iPr4PCP)Ir catalyzed gas phase dehydrogenation of n-butane [6.1] with propene [6.1 M] as acceptor at 200 C. on various solid supports. Florisil was found to give the best results with the dehydrogenation occurring at a rate of 4250 TOh.sup.1. Catalytic systems in which the (p-OK-.sup.iPr4PCP)Ir was supported on neutral alumina and silica proceeded much more slowly and resulted in 780 and 450 TOh.sup.1 respectively. More interestingly in addition to the dehydrogenation products GC analysis revealed higher C.sub.7 and C.sub.8 fragments resulting from olefin dimerization. Particularly on using (p-OK-.sup.iPr4PCP)Ir supported on Florisil, C.sub.7 and C.sub.8 dimerized alkene fragments are formed at a rate of 210 and 390 TOh.sup.1.

Example 2

[0059] Catalyst recyclability studies were performed using the catalytic system based on (p-OK-.sup.iPr4PCP)Ir supported on Florisil (Table 2). These studies reveal that the catalyst is highly recyclable, i.e., can be used for numerous cycles, and proceeded at rates of 4260, 960, 300, and 240 TOh.sup.1 in the first, second, third and fourth cycle respectively.

TABLE-US-00002 TABLE 2 Recylability studies of (p-OK-.sup.iPr4PCP)Ir/Florisil catalyzed gas phase dehydrogenation of n-butane [6.1] with propene [6.1M] as acceptor at 200 C. after 10 minutes Total Solid Olefin Butadiene 1-Butene C.sub.7 C.sub.8 Support Cycle TON TON TON TON TON 2 mg First 705 160 105 25 40 Florisil Second 160 35 20 5 10 MgOSiO.sub.2 Third 50 5 10 2 5 Fourth 40 5 5 5 5

[0060] The current invention therefore, provides an efficient alternative to upgrade unproductive and highly abundant low molecular weight alkanes to fuel grade medium weight hydrocarbons by a tandem alkane-dehydrogenation/alkene-dimerization reaction in the gas phase that is catalyzed by pincer ligated iridium catalysts heterogenized on solid supports such as magnesium silicates (for example, MgO.SiO.sub.2 such as Florisil). The catalyst also shows good recyclability.

[0061] Various modifications and alterations of the process disclosed herein will become apparent to those skilled in the art without departing from the scope and spirit of the process disclosed herein. Other objects and advantages will become apparent to those skilled in the art from a review of the preceding description.

[0062] A number of patent documents and non-patent documents are cited in the foregoing specification in order to describe the state of the art to which the process disclosed herein pertains. The entire disclosure of each of the cited documents is incorporated by reference herein.

[0063] Furthermore, the transitional terms comprising, consisting essentially of and consisting of, when used in the appended claims, in original and amended form, serve to indicate what unrecited additional claim elements or steps, if any, are excluded from the scope of the claim(s). The term comprising is intended to be inclusive or open-ended and does not exclude any additional, unrecited element, method, step or material. The term consisting of excludes any element, step or material other than those specified in the claim and, in the latter instance, impurities ordinarily associated with the specified material(s). The term consisting essentially of limits the scope of a claim to the specified elements, steps or material(s) and those that do not materially affect the basic and novel characteristic(s) of the claimed process. All iridium pincer complex catalysts and methods of use thereof embodied herein can, in alternate embodiments, be more specifically defined by any of the transitional terms comprising, consisting essentially of and consisting of.