Manganese catalysts and their use in hydrogenation of ketones

A catalyst comprising a charged or neutral complex of formula (I):

• wherein:
• Mn is a manganese atom or a manganese ion in oxidation state (I) to (VII);
• R1 and R2 are each independently C4-8monocyclic aryl or C3-7monocyclic heteroaryl moieties, optionally substituted one or more times with a first electron donating group;
• -Fc- denotes a ferrocene (bis(η5-cyclopentadienyl)iron) moiety covalently bonded via adjacent carbon atoms of one of the two cyclopentadienyl moieties, and which may be optionally further substituted, in either cyclopentadienyl ring, one or more times with a substituent selected from the group consisting of halo, aliphatic C1-6 hydrocarbyl, trihalomethyl, aryl, heteroaryl, hydroxy, nitro, amino, alkoxy, alkylthio, carboxylate, sulfonate, phosphate, cyano, thio, formyl, ester, acyl, thioacyl, carbamido and sulfonamido;
• —Z— is an alkylene linker of the formula —(CH2)1-6— in which one or more of the hydrogen atoms of the alkylene may be independently substituted with an alkyl, aryl, heteroaryl, hydroxy, nitro, amino, alkoxy, alkylthio or thiol substituent;
• —Nx is a nitrogen-containing heteroaryl moiety, wherein —Nx is substituted one or more times with a second electron donating group and at least one of R1 and R2 are substituted one or more times with the first electron donating group;
• and
• L1-L3 constitute one, two or three ligands in which each of L1-L3 independently represents a monodentate neutral or anionic ligand:
• or one of L1-L3 represents a monodentate neutral or anionic ligand and the other two of L1-L3 together represent a bidentate neutral or anionic ligand;
• or L1-L3 together represent a tridentate neutral or anionic ligand,
• wherein, when the complex of formula (I) is charged, the catalyst comprises one or more additional counterions to balance the charge of the complex.

A compound comprising a charged or neutral complex of formula (I):

• wherein:
• Mn is a manganese atom or a manganese ion in oxidation state (I) to (VII);
• R1 and R2 are each independently C4-8monocyclic aryl or C3-7monocyclic heteroaryl moieties, optionally substituted one or more times with a first electron donating group;
• -Fc- denotes a ferrocene (bis(η5-cyclopentadienyl)iron) moiety covalently bonded via adjacent carbon atoms of one of the two cyclopentadienyl moieties, and which may be optionally further substituted, in either cyclopentadienyl ring, one or more times with a substituent selected from the group consisting of halo, aliphatic C1-6 hydrocarbyl, trihalomethyl, aryl, heteroaryl, hydroxy, nitro, amino, alkoxy, alkylthio, carboxylate, sulfonate, phosphate, cyano, thio, formyl, ester, acyl, thioacyl, carbamido and sulfonamido;
• —Z— is an alkylene linker of the formula —(CH2)1-6— in which one or more of the hydrogen atoms of the alkylene may be independently substituted with an alkyl, aryl, heteroaryl, hydroxy, nitro, amino, alkoxy, alkylthio or thiol substituent;
• —Nx is a nitrogen-containing heteroaryl moiety, wherein —Nx is substituted one or more times with a second electron donating group and at least one of R1 and R2 are substituted one or more times with the first electron donating group;
• and
• L1-L3 constitute one, two or three ligands in which each of L1-L3 independently represents a monodentate neutral or anionic ligand;
• or one of L1-L3 represents a monodentate neutral or anionic ligand and the other two of L1-L3 together represent a bidentate neutral or anionic ligand;
• or L1-L3 together represent a tridentate neutral or anionic ligand,
• wherein, when the complex of formula (I) is charged, the catalyst comprises one or more additional counterions to balance the charge of the complex.