# US 11,305,268 B2 · Hydrogenation and dehydrogenation catalyst, and methods of making and using the same

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- Number: US 11,305,268 B2
- Document ID: US11305268B2
- Status: Granted
- Kind: B2
- Application number: 16/740,764
- Filed: 2020-01-13
- Published: 2020-05-14
- Granted: 2022-04-19
- Earliest claimed: 2011-08-18
- Applicants: Dmitri Goussev; Denis Spasyuk
- Inventors: Dmitri Goussev; Denis Spasyuk
- Web page: https://patentgrep.com/patent/US11305268B2

## CPC

- B01J 31/2471: {with more than one complexing phosphine-P atom}
- B01J 31/20: Carbonyls
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 31/2404: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring}
- B01J 31/2461: {and phosphine-P atoms as ring members in the condensed ring system or in a further ring}
- C01B 3/02: Production of hydrogen; Production of gaseous mixtures containing hydrogen
- C07B 31/00: Reduction in general
- C07C 29/149: with hydrogen or hydrogen-containing gases
- C07C 41/18: by reactions not forming ether-oxygen bonds
- C07C 209/70: by reduction of unsaturated amines
- C07F 9/58: Pyridine rings
- C07F 15/002: {Osmium compounds}
- C07F 15/0046: {Ruthenium compounds}
- C07F 15/0053: {without a metal-carbon linkage}
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- B01J 2231/763: of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
- B01J 2531/0205: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/0238: 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
- B01J 2531/821: Ruthenium
- B01J 2531/825: Osmium
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present application discloses complexes useful as catalysts for organic chemical synthesis including hydrogenation and dehydrogenation of unsaturated compounds or dehydrogenation of substrates. The range of hydrogenation substrate compounds includes esters, lactones, oils and fats, resulting in alcohols, diols, and triols as reaction products. The catalysts of current application can be used to catalyze a hydrogenation reaction under solvent free conditions. The present catalysts also allow the hydrogenation to proceed without added base, and it can be used in place of the conventional reduction methods employing hydrides of the main-group elements. Furthermore, the catalysts of the present application can catalyze a dehydrogenation reaction under homogenous and/or acceptorless conditions. As such, the catalysts provided herein can be useful in substantially reducing cost and improving the environmental profile of manufacturing processes for variety of chemicals.

## Claims

### Claim 1

A complex of Formula II or III
[M(LNN′)Za] (II)
μN[M(LNN′)Za]2 (III)
wherein:
each Z is independently a hydrogen or halogen atom, a C1-C6 alkyl, a hydroxyl, or a C1-C6 alkoxy, a nitrosyl (NO) group, CO, PMe3, PPh3, or CNR, wherein R is an alkyl or an aryl;
M is Ru or Os;
a is 2 or 3;
each LNN′ is a coordinated ligand that is a compound according to:
wherein
L is a phosphine (PR1R2);
the dotted lines simultaneously or independently represent single or double bonds, wherein when a single bond joins the carbon atom or atoms bound to R4 or R5 or both, R4 or R5 or both are additionally bound to an H;
R1 and R2 are each independently H, or a C1-C20 linear alkyl, a C3-C8 cycloalkyl, or a C5-C20 aryl, each of which is optionally substituted;
R3 is H;
R4 is H;
R5 is H;
each X is independently H, a linear C3-C8 alkyl, a branched C3-C8 alkyl, a cyclic C3-C8 alkyl, a C3-C8 alkenyl, or a C5-C8 aryl, each of which is optionally substituted, or OR, F, CI, Br, I or NR2; or when taken together, two of the X groups together form an optionally substituted saturated ring, partially saturated ring, aromatic ring, or heteroaromatic ring;
R is H, a C1-C20 linear alkyl, a C3-C20 branched alkyl, a C3-C8 cycloalkyl, or a C5-C8 aryl, each of which may be optionally substituted;
each n and m is independently 1 or 2;
q is 0 or 1; and
μN indicates that each LNN′ ligand in the complex of Formula (III) includes a nitrogen atom that bridges two M atoms.

### Claim 2 (depends on 1)

The complex of claim 1, wherein in the compound is:

### Claim 3 (depends on 1)

The complex of claim 1, wherein LNN′ is

### Claim 4 (depends on 1)

The complex of claim 1 which has the structure of any one of

### Claim 5 (depends on 1)

A process for hydrogenation of a substrate comprising treating the substrate with a catalytic amount of a complex of Formula II or III
[M(LNN′)Za] (II)
μN[M(LNN′)Za]2 (III)
according to claim 1 in the presence of molecular hydrogen,
wherein the hydrogenation is performed at a temperature in a range from 40° C. to 100° C. for a time in a range of 1 to 22 hours, and under 50 Bar pressure.

### Claim 6 (depends on 5)

The process of claim 5, wherein the substrate comprises at least one ester; and/or
wherein the process proceeds in the presence of molecular hydrogen according to one of the following schemes
wherein G1 and G2, simultaneously or independently, represent a linear C1-C40 or branched or cyclic C3-C40 alkyl, alkenyl or aromatic group, any of which may be optionally substituted.

### Claim 7 (depends on 5)

The process of claim 5, wherein the substrate and product pair of the hydrogenation reaction comprises:
Hydrogenation Substrate
Product
ester
alcohol
lactone
diol.

### Claim 8 (depends on 5)

The process of claim 5, which is a solvent-free process.

### Claim 9 (depends on 1)

A process for producing ethyl acetate comprising treating ethanol with a catalytic amount of a complex of Formula II or III
[M(LNN′)Za] (II)
μN[M(LNN′)Za]2 (III)
according to claim 1.