Catalysts

Abstract

The present invention concerns the synthesis of dry powdered manganese complexes using spray-drying or freeze-drying methods.

1 - 34 . (canceled) 
     
     
         35 . A powder comprising:
 (a) a manganese transition metal catalyst of a ligand of formula (I):   
       
         
           
           
               
               
           
         
       
       wherein: 
       
         
           
           
               
               
           
         
         p is 3; 
         R is independently selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, CH 2 CH 2 OH, CH 2 COOH and pyridin-2-ylmethyl, or one of R is linked to the N of another Q from another ring via an ethylene bridge; and 
         R 1 , R 2 , R 3 , and R 4  are independently selected from the group consisting of H, C 1 -C 4 -alkyl, and C 1 -C 4 -alkylhydroxy, 
         (b) less than 14 wt % of water, and 
         (c) a non-coordinating counterion of the manganese transition metal catalyst, wherein said non-coordinating counterion is selected from the group consisting of: chloride, bromide, sulfate, nitrate, acetate, and benzoate, 
       
       wherein the powder comprises between 5 and 95 wt % of an inert salt. 
     
     
         36 . The powder of  claim 35 , wherein the powder comprises less than 12 wt % water. 
     
     
         37 . The powder of  claim 35 , wherein the powder comprises less than 10 wt % water. 
     
     
         38 . The powder of  claim 35 , wherein the powder comprises less than 6 wt % water. 
     
     
         39 . The powder of  claim 35 , wherein the inert salt is NaCl. 
     
     
         40 . The powder of  claim 39 , which comprises between 25 and 75 wt % NaCl. 
     
     
         41 . The powder of  claim 35 , wherein the ligand of the catalyst is selected from the group consisting of 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) and 1,2-bis-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane (Me 4 -DTNE). 
     
     
         42 . The powder of  claim 35 , wherein the catalyst is a salt of the metal complexes [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ] 2+ , [(Mn III ) 2 (μ-O)(μ-CH 3 COO) 2 (Me 3 -TACN) 2 )] 2+  or [Mn III Mn IV (μ-O) 2 (μ-CH 3 COO)(Me 4 -DTNE)] 2+ . 
     
     
         43 . The powder of  claim 35 , wherein the catalyst has a non-coordinating counterion selected to provide a preformed transition-metal catalyst that has a water solubility of at least 30 g/l at 20° C. 
     
     
         44 . (canceled) 
     
     
         45 . The powder of  claim 35 , wherein the catalyst is selected from the group consisting of [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ]SO 4 , [Mn III Mn IV (μ-O) 2 (μ-CH 3 COO)(Me 4 -DTNE)]Cl 2 , [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ](CH 3 COO) 2 , [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ](NO 3 ) 2  and [Mn III Mn IV (μ-O) 2 (μ-CH 3 COO)(Me 4 -DTNE)](NO 3 ) 2 . 
     
     
         46 - 47 . (canceled) 
     
     
         48 . A method of preparing a powder comprising:
 (a) a manganese transition metal catalyst of a ligand of formula (I):   
       
         
           
           
               
               
           
         
       
       wherein: 
       
         
           
           
               
               
           
         
         p is 3; 
         R is independently selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, CH 2 CH 2 OH, CH 2 COOH and pyridin-2-ylmethyl, or one of R is linked to the N of another Q from another ring via an ethylene bridge; and 
         R 1 , R 2 , R 3 , and R 4  are independently selected from the group consisting of H, C 1 -C 4 -alkyl, and C 1 -C 4 -alkylhydroxy, 
         (b) less than 14 wt % of water, and 
         (c) a non-coordinating counterion of the manganese transition metal catalyst, wherein said non-coordinating counterion is selected from the group consisting of: chloride, bromide, sulfate, nitrate, acetate, and benzoate, 
       
       wherein the powder comprises between 5 and 95 wt % of an inert salt, the method comprising spray-drying or freeze-drying a mixture comprising the catalyst wherein the mixture comprises more than 20% water. 
     
     
         49 . The method of  claim 48 , wherein the powder comprises less than 12 wt % water. 
     
     
         50 . (canceled) 
     
     
         51 . The method of  claim 48 , wherein the method further comprises a synthesis of the catalyst, prior to the spray-drying or freeze-drying, in which a complexation between manganese ion(s) and the ligand of formula (I) is effected in a complexation mixture comprising more than 6 wt % of water. 
     
     
         52 - 53 . (canceled) 
     
     
         54 . The method of  claim 48 , wherein the ligand is selected from the group consisting of 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) and 1,2-bis-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane (Me 4 -DTNE). 
     
     
         55 . The method of  claim 48 , wherein the catalyst is a salt of the metal complexes [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ] 2+ , [(Mn III ) 2 (μ-CH 3 COO) 2 (Me 3 -TACN) 2 )] 2+  or [Mn III Mn IV (μ-O) 2 (μ-CH 3 COO)(Me 4 -DTNE)] 2+ . 
     
     
         56 - 57 . (canceled) 
     
     
         58 . The method of  claim 48 , wherein the catalyst is selected from the group consisting of [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ]SO 4 , [Mn III Mn IV (μ-O) 2 (μ-CH 3 COO)(Me 4 -DTNE)]Cl 2 , [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ](CH 3 COO) 2 , [(Mn IV ) 2 (μ-O) 3 (Me 3 -TACN) 2 ](NO 3 ) 2  and [Mn III Mn IV (μ-O) 2 (μ-CH 3 COO)(Me 4 -DTNE)](NO 3 ) 2 . 
     
     
         59 - 60 . (canceled) 
     
     
         61 . The method of  claim 48 , wherein the spray-drying or freeze-drying is of an aqueous mixture. 
     
     
         62 . The method of  claim 48 , wherein the spray-drying or freeze-drying is of a solution. 
     
     
         63 - 65 . (canceled) 
     
     
         66 . The method of  claim 48 , wherein the mixture that is spray-dried further comprises an inorganic salt. 
     
     
         67 . (canceled) 
     
     
         68 . The method of  claim 66 , wherein the salt is sodium chloride.