Methods for the reduction of carbon dioxide

A method for producing formate from carbon dioxide comprising

• contacting carbon dioxide with a composition, where the composition comprises (a) a compound selected from Formula (I), salts, optical isomers, geometric isomers, salts of isomers, derivatives thereof, and solvent associated complexes thereof, (b) a solution solvent, and (c) an acid;
• wherein
• Formula (I) is
• R1 is monovalent H, halogen, —CN, nitro (—NO2), —NH2, —N(CH3)2, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which —NH2, —N(CH3)2, methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
• R2 can be monovalent H, halogen, —CN, nitro (—NO2), —NH2, —N(CH3)2, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which —NH2, —N(CH3)2, methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
• R3 can be monovalent H, halogen, —CN, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
• R4 can be monovalent H, halogen, —CN, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluorinated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
• R3 and R4 are optionally bonded together to form a ring, where the ring that is formed can be cycloalkyl, heterocyclyl, aryl, or heteroaryl, which cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluorinated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
• and
• M is iron (Fe), nickel (Ni), palladium (Pd), cadmium (Cd), manganese (Mn), cobalt (Co), copper (Cu), gallium (Ga), or zinc (Zn).