Catalysts and methods for catalytic oxidation

Abstract

Catalytic systems and methods for oxidizing materials in the presence of metal catalysts (preferably manganese-containing catalysts) complexed with selected macropolycyclic rigid ligands, preferably cross-bridged macropolycyclic ligands. Included are using these metal catalysts in such processes as: synthetic organic oxidation reactions such as oxidation of organic functional groups, hydrocarbons, and heteroatoms, including enantiomeric epoxidation of alkenes, enynes, sulfides to sulfones and the like; oxidation of oxidizable compounds (e.g., stains) on surfaces such as fabrics, dishes, countertops, dentures and the like; oxidation of oxidizable compounds in solution, dye transfer inhibition in the laundering of fabrics; and further in the bleaching of pulp and paper products.

1 . A metal complex comprising: 
 (A) a transition metal atom selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(Ell), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV); and    (B) a cross-bridged macropolycyclic ligand comprising; 
 (1) an organic macrocycle ring that comprises at least 4 donor atoms, 2 of said donor atoms being non-adjacent donor atoms; and  
 (2) a moiety that comprises a cross-bridged chain that covalently connects at least 2 non-adjacent donor atoms of said organic macrocycle ring, said covalently connected donor atoms being donor atoms that are coordinated to said transition metal; said cross-bridged chain comprising from 2 to about 5 atoms.  
   
     
     
         2 . A metal complex comprising: 
 (A) a transition metal atom selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(II), Fe(IV), Co(I), Co(II), Co(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(II), and Ru(IV);    (B) a cross-bridged macropolycyclic ligand comprising: 
 (1) an organic macrocycle ring comprising: 
 (i) at least 4 donor atoms independently selected from the group consisting of N, O, S, and P; 2 to 6 of said donor atoms being coordinated to the same transition metal atom; and  
 (ii) a sufficient number of non-donor atoms to separate said donor atoms from each other by covalent linkages of at least one non-donor atom; and  
 
 (2) a moiety that comprises a cross-bridged chain, said cross-bridged chain comprising from 2 to 5 atoms and covalently connecting at least 2 non-adjacent, transition metal atom coordinated, donor atoms of said organic macrocycle ring;  
 said cross-bridged macropolycyclic ligand being coordinated by at least 4 of said donor atoms to said transition metal atom; and  
   (C) when said cross-bridged macropolycyclic ligand comprises less than 6 donor atoms coordinated to said transition metal, a sufficient number of non-macropolycyclic ligands to complete the coordination sphere of said transition metal atom; and    (D) when said transition metals' charge is not neutralized by said non-macropolycyclic ligands, a sufficient number of counter ions to provide said metal complex with charge neutrality.    
     
     
         3 . The metal complex of  claim 2  wherein each counter ion is selected from the group consisting of tosylate, Cl − , PF 6   − , ClO 4   − , BF 4   −  and CF 3 OSO 3   − .  
     
     
         4 . The metal complex of  claim 2  comprising one or more transition metal atoms selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV) and mixtures thereof.  
     
     
         5 . The metal complex of  claim 2  wherein at least one of said non-macropolycyclic ligands is covalently bound to said cross-bridged macropolycyclic ligand or at least one of said non-macropolycyclic ligands is covalently bound to an alkyl group that is covalently bound to said cross-bridged macropolycyclic ligand.  
     
     
         6 . The metal complex of  claim 5  wherein at least one of said non-macropolycyclic ligands is covalently bound to at least one non-donor atom of said organic macrocycle ring.  
     
     
         7 . The metal complex of  claim 5  wherein said non-macropolycyclic ligands are independently selected from the group consisting of ROH, NR 3 , RCN, RS − , RO − , RCOO − , NR 2 H, NRH 2  and RC(O)O −  wherein R is substituted alkyl, unsubstituted alkyl, substituted aryl or unsubstituted aryl; and organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles, and thiazoles.  
     
     
         8 . The metal complex of  claim 2  wherein said non-macropolycyclic ligands are independently selected from the group consisting of ROH, NR 3 , NRH 2 , NR 2 H, RCN, RS − , RO − , RCOO − , RC(O)O −  wherein R is substituted alkyl, unsubstituted alkyl, substituted aryl or unsubstituted aryl; and H 2 O, OH − , OOH − , OCN − , SCN − , N 3   − , CN − , F − , Cl − , Br − , I − , O 2   − , NO 3   − , NO 2   − , SO 4   2− , SO 3   2− , PO 4   3− , HCO 2   − , NH 3 , organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles, and thiazoles.  
     
     
         9 . The metal complex of  claim 2  comprising from 4 to 6 donor atoms.  
     
     
         10 . The metal complex of  claim 2  wherein said donor atoms are independently selected from the group consisting of N and O.  
     
     
         11 . The metal complex of  claim 10  wherein said donor atoms are N.  
     
     
         12 . The metal complex of  claim 2  wherein at least 3 of said donor atoms are N.  
     
     
         13 . The metal complex of  claim 2  comprising 4 or 5 donor atoms, said donor atoms being coordinated to the same transition metal atom.  
     
     
         14 . The metal complex of  claim 13  comprising 4 donor atoms.  
     
     
         15 . The metal complex of  claim 13  comprising 5 donor atoms, said donor atoms being N.  
     
     
         16 . The metal complex of  claim 2  comprising a single transition metal atom.  
     
     
         17 . The metal complex of  claim 2  wherein at least 4 of the donor atoms in the cross-bridged macropolycyclic ligand, form an apical bond angle, D-M-D, with the same transition metal atom, M, of 180±50° and at least one equatorial bond angle, D-M-D, of 90±20°.  
     
     
         18 . The metal complex of  claim 2  having a coordination geometry selected from the group consisting of distorted octahedral and distorted trigonal prismatic, and wherein the cross-bridged macropolycyclic ligand is in a folded conformation.  
     
     
         19 . The metal complex of  claim 2  wherein 2 of the donor atoms in the cross-bridged macropolycyclic ligand occupy mutually trans positions with respect to the coordination geometry about the metal, and at least 2 of the donor atoms in the cross-bridged macropolycyclic ligand occupy mutually cis-equatorial positions of the coordination geometry.  
     
     
         20 . The metal complex of  claim 2  wherein said organic macrocycle ring comprises at least 12 atoms.  
     
     
         21 . The metal complex of  claim 8  comprising: 
 (a) a single transition metal atom selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), and Fe(IV); and    (b) said organic macrocycle ring comprises 4 or 5 donor atoms independently selected from the group consisting of N and 0; said donor atoms being coordinated to said single transition metal atom.    
     
     
         22 . The metal complex of  claim 21  comprising: 
 (a) at least one non-macropolycyclic ligand independently selected from the group consisting of tosylate, NO 3   − , Cl − , Br − , H 2 O, OH − , CH 3 C(O)O − , HC(O)O − , SO 4   2− , PO 4   3− , CH 3 OSO 3− , CH 3 CH 2 OSO 3   − , CH 3 SO 3  and CH 3 CH 2 SO 3   − ; and    (b) 2 pendant moieties independently selected from the group consisting of methyl, ethyl and propyl; and wherein    (c) said organic macrocycle ring comprises 4 N donor atoms, 2 of said donor atoms being non-adjacent bridgehead donor atoms; said donor atoms being separated by 2 or 3 non-donor atoms;    (d) said pendant moieties are covalently bound to said non-adjacent non-bridgehead N donor atoms; and    (e) said cross-bridged chain is selected from the group consisting of ethylene, propylene, 2-butenylene and o-xylylene.    
     
     
         23 . The metal complex of  claim 21  comprising at least one non-macropolycyclic ligand independently selected from the group consisting of carboxymethyl, 2-hydroxybenzyl and 2-picolyl, and wherein 
 (a) said organic macrocycle ring comprises 4 N donor atoms, 2 of said donor atoms being non-adjacent bridgehead donor atoms; said donor atoms being separated by 2 or 3 non-donor atoms;    (b) said non-macropolycyclic ligand is covalently bound to 1 of said non-adjacent non-bridgehead N donor atoms; and    (c) said cross-bridged chain is selected from the group consisting of ethylene, propylene, 2-butenylene and o-xylylene.    
     
     
         24 . The metal complex of  claim 21  wherein at least one non-macropolycyclic ligand is covalently bound to said cross-bridged macropolycyclic ligand.  
     
     
         25 . The metal complex of  claim 2  comprising one or more pendant moieties that are covalently bound to said cross-bridged macropolycyclic ligand; one or more of said pendant moieties being optionally bound to said transition metal.  
     
     
         26 . The metal complex of  claim 25  wherein said one or more pendant moieties are independently selected from the group consisting of H, substituted alkyl, unsubstituted alkyl, substituted aryl or unsubstituted aryl.  
     
     
         27 . The metal complex of  claim 25  wherein one or more of said pendant moieties is bound to a donor atom in the organic macrocycle ring.  
     
     
         28 . The metal complex of  claim 25  comprising one or more transition metal atoms selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV) and mixtures thereof.  
     
     
         29 . The metal complex of  claim 25  comprising only one transition metal atom per complex.  
     
     
         30 . The metal complex of  claim 25  comprising a tetradentate or pentadentate cross-bridged macropolycyclic ligand.  
     
     
         31 . The metal complex of  claim 25  wherein all the donor atoms in the cross-bridged macropolycyclic ligand are selected from the group consisting of N and O.  
     
     
         32 . The metal complex of  claim 25  wherein the cross-bridged macropolycyclic ligand comprises 4 or 5 donor atoms, all of which are coordinated to the same transition metal atom.  
     
     
         33 . The metal complex of  claim 25  wherein the cross-bridged macropolycyclic ligand comprises 4 nitrogen donor atoms all of which are coordinated to the same transition metal atom.  
     
     
         34 . The metal complex of  claim 25  wherein the cross-bridged macropolycyclic ligand comprises 5 nitrogen atoms all of which are coordinated to the same transition metal atom.  
     
     
         35 . The metal complex of  claim 25  wherein at least 2 of the donor atoms in said metal complex's macrocycle ring form an apical bond angle, D-M-D, with the same transition metal atom, M, of 180±50° and at least 2 of which form one equatorial bond angle of 90±20°.  
     
     
         36 . The metal complex of  claim 25  having a coordination geometry selected from the group consisting of distorted octahedral and distorted trigonal prismatic, and wherein the cross-bridged macropolycyclic ligand is in a folded conformation.  
     
     
         37 . The metal complex of  claim 25  wherein 2 of the donor atoms in the cross-bridged macropolycyclic ligand occupy mutually trans positions of the coordination geometry and at least 2 of the donor atoms in the cross-bridged macropolycyclic ligand, occupy cis-equatorial positions of the coordination geometry.  
     
     
         38 . The metal complex of  claim 25  comprising one or two non-macropolycyclic ligands.  
     
     
         39 . The metal complex of  claim 25  wherein said metal complex's organic macrocycle ring comprises at least 12 atoms.  
     
     
         40 . A metal complex comprising Mn(II), Mn(III), Mn(IV), or Mn(V); and a cross-bridged ligand having the formula:  
       
         
           
           
               
               
           
         
       
       wherein in this formula: 
 each “n” is an integer independently selected from 1 and 2, completing the valence of the carbon atom to which the R moieties are covalently bonded;  
 each “R” and “R 1 ” is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, alkylaryl alkylheteroaryl and heteroaryl, or R and/or R 1  are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring; said moieties, except for H, being linear or branched and substituted or unsubstituted;  
 each “a” is an integer independently selected from 2 or 3.  
 
     
     
         41 . A metal complex comprising Mn(II), Mn(III), Mn(IV), or Mn(V); and a cross-bridged ligand having the formula:  
       
         
           
           
               
               
           
         
       
       wherein “R 1 ” is independently selected from the group consisting of H, C 1 -C 20  alkyl, alkenyl and alkynyl; said C 1 -C 20  alkyl, alkenyl and alkynyl moieties being linear or branched and substituted or unsubstituted.  
     
     
         42 . A metal complex comprising a transition metal atom selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Cr(II), Cr(III), Cr(IV), Cr(V), and Cr(VI); and a cross-bridged ligand having the formula:  
       
         
           
           
               
               
           
         
       
       wherein m and n are integers from 0 to 2, p is an integer from 1 to 4, and A is a nonhydrogen moiety having no aromatic content.  
     
     
         43 . The metal complex according to  claim 42  wherein each A is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C 5 -C 20  alkyl.  
     
     
         44 . A metal complex comprising a transition metal atom selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Cr(II), Cr(III), Cr(IV), Cr(V), and Cr(VI); and a cross-bridged macropolycyclic ligand having the formula:  
       
         
           
           
               
               
           
         
       
       wherein “R 1 ” is independently selected from the group consisting of H, C 1 -C 20  alkyl, alkenyl and alkynyl; said C 1 -C 20  alkyl, alkenyl and alkynyl moieties being linear or branched and substituted or unsubstituted; R 2  is selected from the group consisting of ethylene, propylene, 2-butenylene and o-xylylene; and all nitrogen atoms in the macropolycyclic rings are coordinated to the transition metal atom.