Catalyst compositions for hydroformylation and methods of use thereof

Inactive Publication Date: 2021-09-23
BOARD OF SUPERVISORS OF LOUISIANA STATE UNIV & AGRI & MECHANICAL COLLEGE
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0005]In accordance with the purpose(s) of the disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to compositions comprising cationic transition metal phosphine complexes, both mono- and bimetallic, e.g., a cobalt phosphine complex, that can be used to catalyze hy

Problems solved by technology

HCo(CO)4 is considered the most active cobalt catalyst system known, but has a major weakness in that it decomposes to inactive cobalt metal unless high enough pressures of CO gas are used.
On

Method used

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  • Catalyst compositions for hydroformylation and methods of use thereof
  • Catalyst compositions for hydroformylation and methods of use thereof
  • Catalyst compositions for hydroformylation and methods of use thereof

Examples

Experimental program
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Effect test

example 1

droformylation of 1-Alkenes

[0131]Cationic monometallic and bimetallic bis(phosphine)-chelated cobalt catalysts that perform hydroformylation under far lower temperatures and pressures than known systems using neutral cobalt catalysts, and with far higher activities, have been identified and are described herein. An exemplary hydroformylation reaction is shown in FIG. 1. The catalysts of the present disclosure are also active in alkene isomerization with little alkene hydrogenation observed, which is desirable for current processes. The catalysts partially convert aldehydes generated from hydroformylation into desired alcohol products in the presence of hydrogen. Though linear to branched (L:B) regioselectivities of 0.8:1 to 1.4:1 were observed in the aldehyde products derived from 1-alkenes, the chelating bisphosphine ligand may be modified to yield higher aldehyde L:B ratios with 1-alkenes.

[0132]The development of dicationic dicobalt catalysts are based on the stronger coordinating...

example 2

droformylation of Internal Branched Alkenes

[0135]The cationic cobalt catalysts described herein have excellent activity and much higher L:B selectivity for difficult to hydroformylate internal branched alkenes like 2-methyl-2-butene. Hydroformylation runs with 2-methyl-2-butene were done with [Co(acac)(dppe)](BF4), dppe=Et2PCH2CH2PEt2, and Rh(acac)(CO)2+PPh3. The following reaction conditions were utilized: (a) HRh(CO)(PPh3)2: 1 mM Rh(acac)(CO)2, 0.4 M PPh3, 400:1 PPh3:Rh, 1 M 2-methyl-2-butene, 100° C., 7.9 bar, 1:1 H2 / CO in toluene; and (b) [HCo(CO)(dppe)](BF4): 1 mM [Co(acac)(dppe)](BF4), 1 M 2-methyl-2-butene, 140° C., 34.5 bar, 1:1 H2 / CO in t-glyme. Using the foregoing, it was observed that there was no hydroformylation activity by the industrial Rh / PPh3 catalyst, no observed alkene isomerization and no alkene hydrogenation. The cationic cobalt-dppe catalyst did 286 turnovers after 3 hours (28.6% conversion) with 11:1 L:B (based on NMR and GC / MS). Less than 1% alkene hydrogenat...

example 3

ative Active Catalysts

[0136]A variety of chelating bisphosphine ligands were examined for their effect on the hydroformylation activity and selectivity of the monometallic cationic Co(II) catalyst system (BF4− counter-anion, other non-coordination anions should work well). The initial hypothesis was that the extremely strong chelate effect of 1,2-phenylene-linked bisphosphines was critically important in stabilizing the low-spin, cationic Co(II) oxidation state; however, further studies demonstrated that other chelating bisphosphine ligands work well. The strength of the bisphosphine chelate, is clearly important for the overall catalyst stability, but the effect of the phosphine R-groups is even more dramatic.

[0137]The following phosphines have been tested using the cationic cobalt(II) acac catalyst precursor motif. The most successful ligands, which have a bridging 1,2-phenylene or saturated alkyl group, generate active cationic Co(II) hydroformylation catalysts. All have similar ...

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Abstract

Disclosed are highly active cationic cobalt phosphine complexes, both mono- and bimetallic, that can catalyze hydroformylation reactions. The disclosed catalysts can be utilized in methods that provide reaction processes that are hundreds of times faster than high pressure HCo(CO)4 or phosphine-modified HCo(CO)3(PR3) catalysts and operate at considerably lower pressures and temperatures. Also disclosed are methods of hydroformylation using the described transition metal complexes. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS[0001]This Application claims the benefit of U.S. Provisional Application No. 62 / 682,192, filed on Jun. 8, 2018, which is incorporated herein by reference in its entirety.BACKGROUND OF THE DISCLOSURE[0002]Hydroformylation is a reaction that converts alkenes, CO, and H2 into aldehyde products with linear and branched regioselectivities. Side reactions include alkene isomerization and hydrogenation. ExxonMobil has a hydroformylation plant in Baton Rouge that uses the well-known HCo(CO)4 catalyst system, which was originally discovered by Otto Roelen in Germany in 1938. HCo(CO)4 is considered the most active cobalt catalyst system known, but has a major weakness in that it decomposes to inactive cobalt metal unless high enough pressures of CO gas are used. As the temperature of the reaction increases, the CO partial pressure used must increase logarithmically in order to keep HCo(CO)4 from decomposing to cobalt metal. ExxonMobil runs their hydrofo...

Claims

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Application Information

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IPC IPC(8): B01J31/24
CPCB01J31/2409B01J2531/0216B01J2531/845B01J2231/321B01J31/24B01J2531/822B01J2531/82B01J2531/84C07F15/008C07F15/065
Inventor STANLEY, GEORGE GEOFFREYHOOD, DREW MICHAEL
Owner BOARD OF SUPERVISORS OF LOUISIANA STATE UNIV & AGRI & MECHANICAL COLLEGE
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