Cyclic supported catalysts

Compound of general formula (I):

• in which:
• n represents an integer from 7 to 20 or greater than 20, or 21 to 220,
• X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl,
• R1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl,
• Mm+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5,
• L consists of one or more neutral ligands or negatively charged linked to the metal, and
• said compound has the formula (IA) in which t is 0 and Z represents a group Q selected from the group consisting of phosphorus ligands, or the phosphonites and phosphinites, with the exception of phosphines and phosphine oxides, N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, or salen ligands,
• said compound has the formula (IB) in which t is 0 and Z represents a group Q′, a precursor of a group Q selected from the group consisting of azoliums, or 1,3-imidazolium, 1,3-imidazolinium, 1,3-benzimidazolium, 1,2,4-triazolium, 1,3-thiazolium, precursors of phosphorus ligands with the exception of phosphines and phosphine oxides, or chalcogenides, or phosphine sulfides, or salen ligands precursors, or derivatives of salicylaldehyde,
• said compound has the formula (IC) wherein t is 1 and Z represents a group Q selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4 triazolylidenes and 1,3-thiazolylidenes, or salen ligands.

Method of catalyzing a reaction selected from the group consisting of reduction reactions, or reduction reactions in the presence of H2 or the hydrogenation of carbonyl, alkene, alkyne or arene, the oxidation reactions, or oxidation reactions in the presence of O2, the carbon-carbon bond forming reactions, or the Suzuki reaction, Heck, Stille, Kumada and Sonogashira, the carbon-heteroatom bond forming reactions, or carbon-nitrogen, carbon-oxygen, carbon-phosphorus, and carbon-sulfur bond formation, carbonylation reactions in the presence CO, or Fischer-Tropsch, the gas phase carboxylation of reactions in the presence of CO2, and asymmetric catalysis reactions, or the epoxide opening reactions or asymmetric catalysis reactions allowing C—C or C—X bond formation, wherein the catalyst is a compound of formula (IC):

• in which:
• n represents an integer from 7 to 20 or greater than 20, or 21 to 220,
• X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl,
• R1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl,
• Mm+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5,
• L consists of one or more neutral ligands or negatively charged linked to the metal,
• Z is selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4 triazolylidenes and 1,3-thiazolylidenes, or salen ligands.

Method for preparing a compound of formula (IA):

• wherein
• n represents an integer from 7 to 20 or greater than 20, or 21 to 220,
• X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl,
• R1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl,
• Q is a phosphorus ligand, or a secondary phosphonite, or a secondary phosphinite other than a phosphine and phosphine oxide,
• or
• a compound of formula (IB):
• wherein
• n represents an integer from 7 to 20 or greater than 20, or 21 to 220,
• X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl,
• R1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl,
• wherein Q′ is selected from the group consisting of azoliums, or 1,3-imidazolium, 1,3-imidazolinium, 1,3-benzimidazolium, 1,2,4-triazolium, 1,3-thiazolium
• comprising a step of contacting a compound of formula (II):
• in which:
• n represents an integer from 7 to 20 or greater than 20, or 21 to 220,
• X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl,
• R1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl,
• V represents a leaving group, or chosen from the group consisting of halogens, or Cl, Br and I and sulfonates, or OSO2Me, OSO2(C7H7) and OSO2CF3,
• with a compound of formula QA wherein Q is selected from the group consisting of phosphorus ligands, or a secondary phosphonite, or secondary, with the exception of phosphines and phosphine oxides and A represents an alkali metal selected from the group consisting of Na, K and Li or a is H and the reaction is carried out in the presence of a base, to give a compound of formula (IA),
• or with a compound of formula Q′ selected from the group consisting of azoles, or 1,3-imidazoles, 1,3-imidazoline, 1,3-benzimidazoles, 1,2,4-triazoles and 1,3-thiazoles,
• or,
• a compound of formula (IC):
• in which:
• n represents an integer from 7 to 20 or greater than 20, or 21 to 220,
• X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl,
• R1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl,
• Mm+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5,
• L consists of one or more neutral ligands or negatively charged linked to the metal,
• Z represents a group Q selected from the group consisting of phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes,
• comprising a step of contacting a compound of formula (IA),
• said compound (IA) has the formula (I) wherein t is 0 and Z represents a group Q selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes,
• with a metal complex of formula (L′)Mn+ where Mm+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, or 0, 1, 2 or 3, and L′ is comprised of 0, one or more neutral or negatively charged ligands bound to the metal.