Title: Catalytic hydrogenation using complexes of base metals with tridentate ligands

Abstract

Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

Inventors:

Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.

Issue Date:

2016-09-06

Research Org.:

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1322059

Patent Number(s):

9434666

Application Number:

13/587,717

Assignee:

Los Alamos National Security, LLC (Los Alamos, NM)

Patent Classifications (CPCs):

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

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C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C41/26 - by introduction of hydroxy or O-metal groups

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J2231/646 - of aromatic or heteroaromatic rings

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C29/141 - with hydrogen or hydrogen-containing gases

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

C07F15/065 - {without a metal-carbon linkage}

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C41/20 - by hydrogenation of carbon-to-carbon double or triple bonds
C07C211/27 - having amino groups linked to the six-membered aromatic ring by saturated carbon chains
C07C211/48 - N-alkylated amines
C07C2603/18 - Fluorenes
C07C17/354 - by hydrogenation
C07C43/205 - the aromatic ring being a non-condensed ring
C07C69/24 - esterified with monohydroxylic compounds
C07C33/24 - polycyclic without condensed ring systems
C07C43/23 - containing hydroxy or O-metal groups

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

C07F5/04 - Esters of boric acids

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C51/36 - by hydrogenation of carbon-to-carbon unsaturated bonds
C07C2531/28 - of the platinum group metals, iron group metals or copper
C07C209/52 - by reduction of imines or imino-ethers

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07D - HETEROCYCLIC COMPOUNDS

C07D211/46 - having a hydrogen atom as the second substituent in position 4

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C53/126 - Acids containing more than four carbon atoms
C07C67/303 - by hydrogenation of unsaturated carbon-to-carbon bonds

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J2231/645 - of C=C or C-C triple bonds

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C29/175 - {with simultaneous reduction of an oxo group}
C07C2603/12 - only one five-membered ring
C07C13/20 - with a cyclohexene ring
C07C13/26 - with an eight-membered ring
C07C2602/42 - the bicyclo ring system containing seven carbon atoms
C07C31/125 - containing five to twenty-two carbon atoms
C07C29/172 - {with the obtention of a fully saturated alcohol}
C07C2531/22 - Organic complexes
C07C2602/08 - the other ring being five-membered, e.g. indane
C07C33/22 - Benzylalcohol
C07C15/02 - Monocyclic hydrocarbons
C07C5/05 - Partial hydrogenation
C07C29/145 - with hydrogen or hydrogen-containing gases
C07C33/20 - monocyclic

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J2231/643 - of R2C=O or R2C=NR

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C35/32 - the condensed ring system being a
C07C2601/18 - with a ring being at least seven-membered
C07C15/073 - Ethylbenzene
C07C5/03 - of non-aromatic carbon-to-carbon double bonds
C07C11/02 - Alkenes
C07C49/403 - of a six-membered ring

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

C07F15/04 - Nickel compounds

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C45/62 - by hydrogenation of carbon-to-carbon double or triple bonds

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07D - HETEROCYCLIC COMPOUNDS

C07D211/02 - Preparation by ring-closure or hydrogenation

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J31/2295 - {Cyclic compounds, e.g. cyclopentadienyls}
B01J31/2476 - {comprising aliphatic or saturated rings}

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2531/14 - of aluminium or boron
C07C35/38 - derived from the fluorene skeleton

Y - NEW / CROSS SECTIONAL TECHNOLOGIES Y02 - TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE Y02P - CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

Y02P20/52 - using catalysts, e.g. selective catalysts

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J2531/0244 - Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C15/085 - Isopropylbenzene
C07C2601/14 - The ring being saturated
C07C43/04 - Saturated ethers
C07C2601/16 - the ring being unsaturated
C07C209/70 - by reduction of unsaturated amines
C07C41/01 - Preparation of ethers

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J2531/845 - Cobalt
B01J31/189 - {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
B01J2531/847 - Nickel

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C13/64 - with a bridged ring system
C07C25/13 - containing fluorine
C07C33/46 - containing only six-membered aromatic rings as cyclic parts

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

C07F15/045 - {without a metal-carbon linkage}

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C41/18 - by reactions not forming ether-oxygen bonds

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

C07F15/06 - Cobalt compounds

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DOE Contract Number:  

AC52-06NA25396

Resource Type:

Patent

Resource Relation:

Patent File Date: 2012 Aug 16

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE