Catalytic systems for the conversion of hydrocarbons to functionalized products

Abstract

This invention discloses methods and processes for selectively converting hydrocarbons such as methane to materials such as alcohols or other materials containing more reactive functionalities.

1 .- 12 . (canceled) 
     
     
         13 . A hydrocarbon conversion process, comprising:
 passing a feed comprising hydrocarbons to a C—H activation zone, comprising a C—H activation catalyst and a solvent, at C—H activation conditions, to form an activated hydrocarbon;   contacting the activated hydrocarbon with a functionalizing agent to produce a functionalized hydrocarbon; and   
       wherein the C—H activation zone comprises a solvent having an acidity level selected from the group consisting of neutral, basic and highly basic, the catalyst comprises one or more transition metal selected from the group consisting of Re, Os, Ir, Ru, W, and Rh, and one or more ligand. 
     
     
         14 . The process of  claim 13  wherein the feed comprises an alkane and the functionalized hydrocarbon is an alcohol. 
     
     
         15 . The process of  claim 14  wherein the alcohol is methane. 
     
     
         16 . The process of  claim 13  wherein the feed comprises an arene and the functionalized hydrocarbon is a phenol. 
     
     
         17 . The process of  claim 16  wherein the feed is benzene. 
     
     
         18 . The process of  claim 13 , wherein said one or more ligand is selected from the group consisting of hydroxy, alkoxy, oxo, carboxylate, optionally substituted diol, optionally substituted catechol, optionally substituted polyol, and optionally substituted acetylacetonate. 
     
     
         19 . The process of  claim 13 , wherein said one or more ligand is selected from the group consisting of ammine, optionally substituted amine, optionally substituted amide, optionally substituted nitrogen heterocycle, optionally substituted chelating diamine, optionally substituted chelating polyamine, optionally substituted chelating amide, and optionally substituted linked nitrogen heterocycle. 
     
     
         20 . The process of  claim 13  wherein the solvent is selected from the group consisting of amine and conjugate base amides, alcohol and conjugate base alkoxide, water-containing hydroxides, and a molten salt mixture. 
     
     
         21 . The process of  claim 13  wherein the activated hydrocarbon comprises a metal-alkyl covalent bond. 
     
     
         22 . A process according to  claim 21  wherein a metal alkyl is converted to a metal alkoxide by the functionalizing agent. 
     
     
         23 . The process of  claim 13  wherein the functionalizing agent is an oxidant comprising an O-atom donor. 
     
     
         24 . The process of  claim 23  wherein the O-atom donor is selected from the group consisting of amine-N-oxide, cupric oxide, iron oxide, periodate (IO4—), vanadate (VO43−), molybdate (MoO42−), nitrous oxide (N2O), hydrogen peroxide (H2O2), selenate (SeO42−), tellurate (TeO42−), hypochlorite (ClO−), chlorite (ClO2—), nitrate (NO3−), and sulfoxides. 
     
     
         25 . A method for activating a hydrocarbon which comprises contacting a C—H bond of the hydrocarbon with a metal ligand complex in a basic medium; and 
       wherein the method does not operate by the generation of free radicals. 
     
     
         26 . The method of  claim 25  wherein the metal ligand complex comprises a transition metal selected from the group consisting of Ir, Os, Re, W, Rh and Ru and a ligand comprises ligating atoms selected from periodic Group IV, V, and VI, or combinations thereof. 
     
     
         27 . A method of  claim 25 , wherein the metal ligand complex comprises one or more ligands selected from the group consisting of hydroxy, alkoxy, oxo, carboxylate, optionally substituted diol, optionally substituted polyol, and optionally substituted acetylacetonate. 
     
     
         28 . A method of  claim 25 , wherein the metal ligand complex comprises one or more ligand selected from the group consisting of ammine, optionally substituted amine, optionally substituted amide, optionally substituted nitrogen heterocycle, optionally substituted chelating diamine, optionally substituted chelating polyamine, optionally substituted chelating amide, and optionally substituted linked nitrogen heterocycle. 
     
     
         29 . A method of  claim 28  wherein the linked nitrogen heterocycle is selected from the group consisting of optionally substituted bipyridine, optionally substituted bipyrazine, and optionally substituted bipyrimidine. 
     
     
         30 . A method of  claim 25  wherein the basic media is a solvent. 
     
     
         31 . A method of  claim 25  wherein the basic media is a solid support. 
     
     
         32 . A method of  claim 30  wherein the solvent is basic. 
     
     
         33 . A method of  claim 30  wherein the solvent is highly basic. 
     
     
         34 . A method according to  claim 32  wherein the solvent is selected from the group consisting of ammine containing the conjugate base amides, alcohols containing the conjugate base alkoxides, water-containing hydroxides, molten salt mixtures such as NaOH/KOH or NaNH2/KNH2. 
     
     
         35 . A method of  claim 25  wherein hydrocarbon activation is accelerated by the basic medium. 
     
     
         36 . A method according to  claim 25  wherein the hydrocarbon is an alkane. 
     
     
         37 . A method according to  claim 37  wherein the alkane is methane. 
     
     
         38 . A method according to  claim 25  wherein the hydrocarbon is an arene. 
     
     
         39 . A method according to  claim 38  wherein the arene is benzene. 
     
     
         40 . A method according to  claim 25  wherein activating a hydrocarbon results in formation of a metal-alkyl covalent bond. 
     
     
         41 . A method of identifying a hydrocarbon C—H bond activation catalyst comprising the steps
 determining a pH value for a candidate metal complex in aqueous solution and selecting those candidates which increase solution pH; 
 determining the Gibbs free energy value for forming a metal alkyl complex from a corresponding metal hydroxy complex and selecting catalysts with values below a threshold value. 
 
     
     
         42 . A method according to  claim 41  wherein the pH value is experimentally determined. 
     
     
         43 . A method according to  claim 41  wherein the pH value is computationally determined. 
     
     
         44 . A method according to  claim 41  wherein the Gibbs free energy value is experimentally determined. 
     
     
         45 . A method according to  claim 41  wherein the Gibbs free energy value is computationally determined. 
     
     
         46 . The method of  claim 41  wherein said threshold value is less than +35 kcal/mol. 
     
     
         47 . A method of identifying a hydrocarbon C—H bond activation catalyst which operates in non acidic media comprising the steps
 contacting a candidate catalyst with a hydrocarbon in a deuterated solvent under activating conditions; 
 detecting deuterium incorporation in the hydrocarbon.