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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
  • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/226—Sulfur, e.g. thiocarbamates
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C231/00—Preparation of carboxylic acid amides
  • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C231/00—Preparation of carboxylic acid amides
  • C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/41—Preparation of salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/60—Reduction reactions, e.g. hydrogenation
  • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/60—Reduction reactions, e.g. hydrogenation
  • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
  • B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/0247—Tripodal ligands, e.g. comprising the tris(pyrazolyl)borate skeleton, "tpz", neutral analogues thereof by CH/BH exchange or anionic analogues of the latter by exchange of one of the pyrazolyl groups for an anionic complexing group such as carboxylate or -R-Cp
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/845—Cobalt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen

Definitions

• the invention relates to a process for the conversion of carbon dioxide or bicarbonates to formic acid derivatives using a catalytic system consisting of a cobalt complex of cobalt salt and at least one tripodal tetradentate ligand.
• the catalyst complex can be used as a homogeneous catalyst.
• the invention also relates to the new cobalt complexes per se.
• the hydrogenation of carbon dioxide (Scheme 1) and bicarbonates (Scheme 2) is usually carried out using transition metal catalysts such as iridium, ruthenium, and rhodium.
• transition metal catalysts such as iridium, ruthenium, and rhodium.
• an iridium (III) catalyst generates 3,500,000 TON (turn over numbers) at 120 ° C and 60 bar CO2 / H2 after a reaction time of 48 hours (Nozaki (R. Tanaka, M. Yamashita, K. Nozaki, J. Chem Chem. Soc., 2009, 131, 14168-14169) using a cationic Cp * Ir (III) catalyst with phenanthroline derivatives as ligands (Y. Himeda, N. Onozawa- Komatsuzaki, H. Sugihara, K. Kasuga, Organometallics 2007, 26, 702-712), a TON for the hydrogenation of carbon dioxide of 222,000 could be achieved.
• the invention therefore an object of the invention to search for inexpensive technically applicable catalyst systems for the implementation of carbon dioxide and bicarbonates, which achieve high activities and under simple reaction conditions, preferably at room temperature, work.
• the invention describes the use of cobalt complexes as catalysts for the production of formic acid and formic acid derivatives using carbon dioxide or bicarbonates at low ( ⁇ 140 ° C) temperatures and preferably under low pressure ( ⁇ 100 bar) in good yields and high conversions.
• the invention also relates to new cobalt complexes.
• the process according to the invention is characterized in that a novel catalyst system comprising a cobalt salt and at least one tripodal tetradentate ligand is used.
• the catalytic system can be used as a homogeneous cobalt complex.
• the catalyst can be separated and reused after a reaction. Over a wide temperature and pressure range, the catalyst is stable.
• a suitable solvent should be used for the operation.
• suitable solvents for the conversion of carbon dioxide or bicarbonates to corresponding formic acid derivatives are selected from the group comprising alcohols, e.g. Methanol, ethanol, isopropanol, ether, e.g. THF, dioxane, MTBE, ETBE, ketones, e.g. Acetone, dibutyl ketone, amines, e.g. Monoethanolamine, amides e.g. NMP, dimethylformamide, dibutylformamide, organic carbonates e.g. For example, propylene carbonate and water.
• alcohols e.g. Methanol, ethanol, isopropanol, ether, e.g. THF, dioxane, MTBE, ETBE, ketones, e.g. Acetone, dibutyl ketone, amines, e.g. Monoethanolamine, amides e.g. NMP, dimethylformamide,
• the resulting formic acid derivative may be any salt.
• the cation may be an organic or inorganic cation, eg Li + , Na + , K + , Ca 2+ , Mg 2 ++ , Al 3+ , Fe 2+ , Co 2+ , Mn 2+ , NH 4 + , NEt 4 + .
• the hydrogenation of carbon dioxide to corresponding formic acid derivatives, such as formic acid-amine adducts, alkyl formates and / or formamides, with the cobalt catalyst system according to the invention are preferably bases, e.g. Alkylamines (tertiary or secondary), preferably tri- or diethylamine, are added.
• the reaction temperatures should generally be between 40 ° C and 140 ° C.
• the preferred temperature range is 60 ° C to 120 ° C. Most preferable is the temperature range 80 ° C to 120 ° C. In the entire proposed temperature range, formic acid derivatives can be generated with high selectivity.
• the pressure on hydrogen should generally be between 5 and 100 bar.
• the catalyst system described may consist of an in situ generated catalyst, cobalt source and ligand, or a previously synthesized cobalt complex.
• a catalyst system according to the invention is used which represents a cobalt complex consisting of a cation and an anion or a neutral cobalt complex having the general formula (Ia) or (Ib),
• X is selected from the group comprising N2, Hb, H, CO, CO2, H2O, halide, acetylacetonate (acac “ ), perchlorate (CIO4 2” ) and sulfate (S0 4 2 “ ), formate, (HCO2 " )
• m means the number 1, 2, 3, 4, 5 or 6; preferably 1, 2 or 3;
• n is the number 1 or 2.
• L represents a tripodal ligand of the general formula (II):
• D and Z are the same or different and selected from the group comprising N, O, P and S;
• R 1, R 2 are the same or different selected from the group comprising alkyl
• R 3 , R 4 identically or differently selected, from the group comprising alkyl (C 1 -C 6), cycloalkyl (C 3 -C 10), aryl or heteroaryl;
• D and / or Z may be coordinated with the cobalt.
• Y " is a monovalent anion selected from the group comprising halides, P (R) 6 “ , S (R) 6 “ , B (R) 4 “ , where R is an alkyl (C1-C6), cycloalkyl (C3) C6), aryl or halogen radical, triflate and mesylate anions.
• R is an alkyl (C1-C6), cycloalkyl (C3) C6), aryl or halogen radical, triflate and mesylate anions.
• Y " BF 4 " , PF 6 “ or BPh 4 " .
• Halogen or halides include Cl, F, Br and I.
• alkyl groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl may occur.
• cycloalkyl groups which may be mentioned are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• Aryl for the purposes of the invention, means aromatic ring systems which may be phenyl, naphthyl, phenanthrenyl and anthracenyl.
• Heteroaryl represents hetero-aromatic ring systems which may be five-membered and six-membered heterocycles in which at least one carbon atom is replaced by nitrogen, oxygen and / or sulfur, preferably pyridine, quinoline, pyrimidine, quinazoline, furan, pyrazole, pyrrole , Imidazole, oxazole, thiophene, thiazole, triazole.
• m is preferably 1 or 2.
• n is preferably 1.
• Preferred ligands of the general formula (II) are those in which D is nitrogen (N) or phosphorus (P). Z is preferably phosphorus (P).
• R3 and R4 are preferably phenyl. q and r are preferably 1.
• Y " is preferably BF 4 " , PF 6 “ or BPh 4 " .
• the invention also provides the catalyst system of the general formulas (Ia) and (Ib) per se, where X, L, m and n have the abovementioned meanings.
• the ligand to be used is a tetradentate ligand coordinated to the cobalt.
• a cobalt source is used as a precatalyst together with a ligand of the general formula (II).
• the cobalt source used may be a Co (0), Co (II) or Co (III) source.
• Preferred sources are cobalt Co (BF 4) 2 -6H 2 0, Co (acac) 2 or Co (acac). 3
• ligands used are T1 or T2.
• the ligand is added in excess or in excess to the cobalt source, preferably the ratio cobalt source: ligand at 1: 1 or with an excess ligand.
• Cobalt complexes of the general formula (la) very particularly preferably employed are in the inventive method, for example, [Co (acac) (T1)] BPh 4, [Co (acac) (T1)] BF 4, [CoH (T1)] BPh 4, [ CoH (T1)] BF 4, [Co (H) 2 (T1)] BPh 4, [Co (H) 2 (T1)] BF 4, [Co (H) 2 (T1)] PF. 6
• the preparation of cobalt catalyst complexes can be carried out as follows:
• a preferably used in situ catalyst system from a Co source preferably cationic Co (BF 4 ) 2 -6H 2 O, and the ligand T1 ligand tris [(2-diphenylphosphino) ethyl] phosphine (T1); MW 670.69052, melting point 134-139 ° C., commercially available from Acros or Sigma Aldrich
• high activities could be achieved in various solvents, bases and under pressures of 5-80 bar, eg for the preparation of sodium formate from sodium bicarbonate (TON 3877).
• Cobalt-catalyzed reactions are generally not transferable to iron-catalyzed reactions, and vice versa.
• the catalyst activity was 6 times higher than the best TON when using an iron catalyst described in the literature and 2 times higher than when using the best noble metal catalyst system.
• the cobalt catalyst system preferably used according to the invention is therefore even superior to previous systems based on the use of noble metal-containing catalyst systems.
• Trifluoromethanesulfonic acid (1 .5 equivalents) is added slowly to the solution changing the color from yellow to dark red. After stirring for 10 minutes, 43 mg of NaBF 4 , (1 .5 equivalents) in 5 mL of distilled ethanol are added. The entire solution is concentrated to about 50% and the complex is precipitated as a red solid. It is filtered and dried in vacuo.
• 1 H NMR: m, ⁇ ⁇ -1 1.10 -1 1 .36
• Alkyl Formates The synthesis of the alkyl formates was analogous to the synthesis of sodium formate, except that 20 ml of the corresponding alcohol and 2 ml of triethylamine were added.
• the reaction mixture is treated in an autoclave with 30 bar C0 2 and 60 bar of hydrogen at room temperature, then heated to 100 ° C and stirred for 20 h. After cooling and releasing the pressure, a GC analysis was carried out.
• Formamide Formation Formamide synthesis was analogous to the sodium formate synthesis except that 0.025 mole of the corresponding amine (dimethylamine, piperidine) was added to 20 mL of MeOH. To the reaction solution then 30 bar of CO2 and 60 bar of hydrogen are pressed and stirred for 20 h at 100 ° C. The analysis was performed by GC with diglyme as an internal standard. The yields were calculated on the amine.

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