Ionic compounds with a delocalized anionic charge, and their use as ion conducting components or as catalysts

Abstract

The invention relates to an ionic compound corresponding to the formula [R 1 X 1 (Z 1 )-Q − X 2 (Z 2 )—R 2 ] m M m+ in which M m+ is a cation of valency m, each of the groups X i is S=Z 3 , S=Z 4 , P—R 3 or P—R 4 ; Q is N, CR 5 , CCN or CSO 2 R 5 , each of the groups Z i is ═O, ═NC≡N, ═C(C≡N) 2 , ═NS(=Z) 2 R 6 or ═C[S(=Z) 2 R 6 ] 2 , each of the groups R i , is Y, YO—, YS—, Y 2 N— or F, Y represents a monovalent organic radical or alternatively Y is a repeating unit of a polymeric frame. The compounds are useful for producing ion conducting materials or electrolytes, as catalysts and for doping polymers.

1 . Ionic compound corresponding to the formula  
       
         
           
           
               
               
           
         
       
       in which: 
 M m+  is a proton or a metal cation having the valency m, chosen from ions of alkali metals, of alkaline-earth metals, of transition metals or of rare-earth metals, or an organic onium cation or an organometallic cation, 1≦m≦3;  
 X 1  and X 2 , denoted below by X i , represent, independently of each other, S=Z 3 , S=Z 4 , P—R 3  or P—R 4 ;  
 Q represents N, CR 5 , CCN or CSO 2 R 5 ;  
 Z 1 , Z 2 , Z 3  and Z 4 , denoted below by Z i , represent, independently of each other, ═O, ═NC≡N, C(C≡N) 2 , NS(=Z) 2 R 6  or ═C[S(=Z) 2 R 6 ] 2 , Z having the same meaning as Z i , it being understood that, in a segment —X 1 -Q-X 2 —, not more than 3 groups Z i  represent ═O;  
 R 1 , R 2 , R 3 , R 4 , R 5  and R 6 , denoted below by R i , represent, independently of each other, Y, YO—, YS—, Y 2 N— or F;  
 Y represents a monovalent organic radical, particularly containing from 1 to 16 carbon atoms, chosen from alkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl, azaalkenyl, aryl, alkylaryl or perfluoroalkyl radicals, or from the radicals obtained from the above-mentioned radicals by substitution, in the chains and/or the aromatic part, with hetero atoms chosen from halogens, oxygen, nitrogen, sulfur or phosphorus; it being understood that sulfur or phosphorus are present, they can optionally be linked to substituted nitrogen or oxygen atoms, or alternatively Y is a repeating unit of a polymeric backbone.  
 
     
     
         2 . Ionic compound according to  claim 1 , characterized in that the cation M m+  is a metal cation chosen from K + , Li + , Mg ++ , Ca ++  or Ba ++ , Cu ++ , Zn ++ , Fe ++  or Re +++ .  
     
     
         3 . Ionic compound according to  claim 1 , characterized in that the cation M m+  is an onium cation chosen from the group consisting of ammonium ions, guanidinium ions, amidinium ions, pyridinium ions, imidazolium ions, imidazolinium ions, triazolium ions, sulfonium ions, iodonium ions, phosphonium ions, nitrosyl and NO 2   + .  
     
     
         4 . Ionic compound according to  claim 1 , characterized in that the cation M m+  is an organometallic cation chosen from metallocenium ions, metal cations coordinated by atoms such as O, S, Se, N, P or As and borne by organic molecules, trialkylsilyl, tetraalkylgermanyl and dialkylstannyl groups in which the alkyl radicals contain from 1 to 10 carbon atoms.  
     
     
         5 . Ionic compound according to  claim 4 , characterized in that the organometallic cation forms part of a polymer chain.  
     
     
         6 . Ionic compound according to  claim 1 , characterized in that the cation M +  is the repeating unit of a conjugate polymer in cationic oxidized form.  
     
     
         7 . Ionic compound according to  claim 1 , characterized in that at least one of the groups Xi represents a phosphorous group.  
     
     
         8 . Ionic compound corresponding to  claim 7 , characterized in that it corresponds to one of the formula  
       
         
           
           
               
               
           
         
       
     
     
         9 . Ionic compound according to  claim 8 , characterized in that Q represents N.  
     
     
         10 . Ionic compound according to  claim 1 , characterized in that the groups X i  represent a group S-Z i .  
     
     
         11 . Ionic compound according to  claim 10 , characterized in that Q represents N, it being understood that if R 1  is CF 3 , R 2  is a phenyl optionally bearing a halogen or an NO 2 , three substituents Z i  represent 0 and one substituent Z i  represents ═NSO 2 CF 3 , then M is other than an alkali metal cation or a proton.  
     
     
         12 . Ionic compound according to  claim 1 , characterized in that the radicals R 1  and R 2  are chosen, independently of each other, from perfluoroalkyl radicals, alkyl radicals, alkenyl radicals, dialkylamino radicals and styrenyl radicals.  
     
     
         13 . Ionic compound according to  claim 12 , characterized in that the perfluoroalkyl radicals contain from 1 to 8 carbon atoms, the alkyl radicals contain from 1 to 8 carbon atoms, the alkenyl radicals contain from 2 to 18 carbon atoms and the alkyl radicals of the dialkylamino groups contain from 1 to 18 carbon atoms.  
     
     
         14 . Ionic compound according to  claim 12 , characterized in that at least two groups Z i  represent ═O, the groups Z i  different from ═O being ═NSO 2 R F , R F  being a perfluoroalkyl group.  
     
     
         15 . Ionic compound according to  claim 1 , characterized in that the groups Z i  represent, independently of each other, ═CO, ═N—C≡N or ═C(C≡N) 2 .  
     
     
         16 . Ionic compound according to  claim 1 , characterized in that Z 1  to Z 3  represent ═O and Z 4  represents ═C[S(=Z) 2 R 6 ] 2 .  
     
     
         17 . Ionic compound according to  claim 1 , characterized in that they correspond to one of the formulae  
       
         
           
           
               
               
           
         
       
       in which R 6  has the same meaning as R 6  and R f  and R′ f  represent a perfluoroalkyl radical.  
     
     
         18 . Ionic compound according to  claim 1 , characterized in that it corresponds to the formula [R 1 SO 2 N—S*═O(R 2 )═NSO 2 R 6 ] −  in which R 1  is different from R 6 .  
     
     
         19 . Ionic compound according to  claim 1 , characterized in that it corresponds to the formula [R 1 SO 2 N—S*═O(R 2 )═N—S*═O(R 5 )═NSO 2 R 6 ] − .  
     
     
         20 . Ionic compound according to  claim 19 , characterized in that R 1  and R 6  represent, independently of each other, a radical chosen from F, CF 3 , C 2 F 5 , C 4 F 9 , C 6 F 13  and C 8 F 17 , and R 2  and R 5  represent, independently of each other, an alkyl, an aryl, an alkylaryl or a dialkylamino preferably containing from 1 to 20 carbon atoms.  
     
     
         21 . Process for preparing a compound according to  claim 1 , characterized in that it consists in reacting a compound R1-X1(Z1)-Q-X2(L)R2 with a compound A2Z2, in which: 
 A is an alkali metal, a proton, an amino or phosphorus-containing base, a trialkylsilyl group, a dialkylstannyl group, LiH, MgCl, Li, MgL1, ZnL1, CdL1, Cu, Mg, Zn, Cd, Hg or a trialkylsilyl, trialkylgermanyl or trialkylstannyl group,    L and L1 are leaving groups.    
     
     
         22 . Process for preparing a compound according to  claim 1 , characterized in that it consists in reacting a compound R 1 —X 1 (Z 1 )-QA2 with a compound L-X 2 (Z 2 )R 2  in which: 
 A is an alkali metal, a proton, an amino or phosphorus-containing base, a trialkylsilyl group, a dialkylstannyl group, LiH, Li, MgL1, ZnL1, CdL1, Cu, Mg, Zn, Cd, Hg or a trialkylsilyl, trialkylgermanyl or trialkylstannyl group,    L and L1 are leaving groups.    
     
     
         23 . Process according to  claim 21 , characterized in that the leaving groups are chosen from halogens, pseudohalogens (including fluorinated or non-fluorinated sulfonates, and imidazoyl, triazolyl and benzotriazole radicals.  
     
     
         24 . Process for preparing a compound according to  claim 1 , in which X 1 (Z 1 ) is identical to X 2 (Z 2 ), characterized in that it consists in reacting an ionic nitride or a metallic derivative of hexamethyl-disilazane or of ammonia in the presence of a base with a precursor containing a leaving group.  
     
     
         25 . Process according to  claim 24 , characterized in that the nitriding agent is Li 3 N, ammonia, its derivatives with silanes and their alkali metal derivatives such as N[SiCH 3 ) 3 ] 2 Li, N[SiCH 3 ) 3 ] 2 Na and N[SiCH 3 ) 3 ] 2 K.  
     
     
         26 . Process for preparing a compound according to  claim 18 , characterized in that it consists in reacting a salt [R 1 SO 2 N═NSO 2 R 2 ] − M′ +  with a halogenating agent, to give the precursor R 1 SO 2 N═NSOR 2 X (X being a halogen), and then in condensing said precursor with a sulfonamide R 3 SO 2 NH 2  in the presence of a base, or with a metallic derivative of sulfonamide such as R 3 SO 2 NLi 2  or R 3 SO 2 NNa 2 , and in carrying out an ion exchange in order to obtain the desired cation.  
     
     
         27 . Ion conducting material consisting of a solution of an ionic compound according to  claim 1 , in a solvent.  
     
     
         28 . Material according to  claim 27 , characterized in that the cation of the ionic compound is chosen from ammonium, lithium, potassium, zinc, calcium, a substituted ammonium, an imidazolium, a triazolium, a pyridinium and a 4-dimethylaminopyridinium, said cations optionally bearing a substituent on the carbon atoms of the ring.  
     
     
         29 . Material according to  claim 27 , characterized in that the solvent is an aprotic liquid solvent.  
     
     
         30 . Ion conducting material according to  claim 27 , characterized in that the solvent is a crosslinked or non-crosslinked solvating polymer, bearing or not bearing grafted ionic groups.  
     
     
         31 . Ion conducting material according to  claim 27 , characterized in that the solvent is a mixture of an aprotic liquid solvent and a polar polymer.  
     
     
         32 . Electrolyte consisting of an ionic compound dissolved in a solvent, characterized in that the ionic compound is a compound according to  claim 1 .  
     
     
         33 . Primary or secondary battery, comprising a negative electrode, a positive electrode and an electrolyte, characterized in that the electrolyte contains an ionic compound according to  claim 1 .  
     
     
         34 . Primary or secondary battery, comprising a negative electrode, a positive electrode and an electrolyte, characterized in that the electrolyte is an ion conducting material according to  claim 29 .  
     
     
         35 . System for modulating light, comprising an electrolyte and electrodes, characterized in that the electrolyte contains an ionic compound according to  claim 1 .  
     
     
         36 . Supercapacitor consisting of an electrolyte and electrodes, characterized in that the electrolyte contains an ionic compound according to  claim 1 .  
     
     
         37 . Process for doping a polymer, which consists in partially oxidizing said polymer in order to create carbocations whose charge is compensated by the anions of an ionic compound, characterized in that the ionic compound is a compound according to  claim 1 .  
     
     
         38 . Process for polymerizing or crosslinking monomers or prepolymers capable of reacting cationically, characterized in that a compound according to  claim 1  is used as a photoinitiating source of acid for catalyzing the reaction.  
     
     
         39 . Use of an ionic compound according to  claim 1 , as a catalyst for polymerization reactions, for condensation reactions, for addition or elimination reactions, for oxidation or reduction reactions, for solvolyses, for Friedel-Crafts reactions and for Diels-Alder reactions.  
     
     
         40 . Use of an ionic compound according to  claim 18 , for the preparation of optically active organic compounds or for enantioselective polymerization reactions.