US4271033A
Expired / Lapsed
US
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Transition metal complex catalysts
Assignee: California Institute of Technology
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Filing: 1979-08-20
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Granted: 1981-06-02
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Expires: 1999-08-20
Abstract
Abstract Substrates are oxidized by means of two-oxidative addition reactions of a dimeric, dinuclear transition metal complex oxidant containing four binucleating diisocyanide bridge ligands. The complex is reoxidized by means of a secondary oxidant which is a stronger oxidizing agent than the complex which in turn is oxidized by molecular oxygen. Though the direct oxidation of the complex by oxygen involves a large energy barrier and is relatively slow, the kinetics of the two stage oxidation of the complex by the secondary oxidant and of the oxidant by oxygen permit regeneration of the oxidant at reasonable rate. Substrates, such as the olefins, ethylene or propylene, have been continuously oxidized by bubbling oxygen and the olefin through a solution of a dimeric, dirhodium complex containing four 1,3-diisocyanopropane bridge ligands and a secondary oxidant such as a cerium salt.
Inventors
- 👤 Harry B. Gray
- 👤 Kent R. Mann
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 00:44
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/18; B01J31/1805; C; C07; C07D; C07D301/00; C07D301/02; C07D301/03; C07D301/04; C07D301/06; C07F; C07F15/00; C07F15/0006; C07F15/0073; C07F15/06; B01J2231/00; B01J2231/70; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/821; B01J2531/822; B01J2531/824; B01J2531/825; B01J2531/827; B01J2531/828; B01J2531/84; B01J2531/842; B01J2531/845; B01J2531/847; B01J2531/90; B01J2531/96; B01J31/40; B01J31/4015; B01J31/4023; B01J31/4038; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/584; Y10; Y10T; Y10T137/00; Y10T137/0318; Y10T137/0324; Y10T137/0329
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
32 words
An oxidizing reagent comprising the combination of a dimeric, dinuclear transition metal complex containing four binucleating diisocyanide bridge ligands and a secondary oxidant which is a stronger oxidizing agent than the complex.
Claim 2
Dependent Claim
32 words
An oxidizing reagent comprising the combination of a dimeric, dinuclear transition metal complex containing four binucleating diisocyanide bridge ligands and a secondary oxidant which is a stronger oxidizing agent than the complex.
Claim 3
Dependent Claim
17 words
A reagent according to claim 1 in which the complex and secondary oxidant are dissolved in solution.
Claim 4
Dependent Claim
14 words
A reagent according to claim 2 in which the solution contains dissolved molecular oxygen.
Claim 5
Dependent Claim
12 words
A reagent according to claim 2 in which the solvent is water.
Claim 6
Dependent Claim
14 words
A reagent according to claim 2 in which the solvent is an organic solvent.
Claim 7
Dependent Claim
15 words
A reagent according to claim 1 in which the metal is a platinum group metal.
Claim 8
Dependent Claim
23 words
A reagent according to claim 6 in which the metal is selected from rhodium, cobalt, iridium, platinum, palladium, nickel, osmium, ruthenium or iron.
Claim 9
Dependent Claim
34 words
A reagent according to claim 6 in which the binucleating biisocyanide is selected from compounds of the formula (CN) 2 R where R is an organic divalent group containing 2 to 20 carbon atoms.
Claim 10
Dependent Claim
19 words
A reagent according to claim 8 in which R is selected from alkylene, arylene, alkarylene, cycloalkylene, alkylcyoalkylene or alkarylene.
Claim 11
Dependent Claim
34 words
A reagent according to claim 9 in which the biisocyanide is selected from 1,3-diisocyanopropane, 1,4-diisocyanobutane, 2,5-dimethyl-2,5-diisocyanohexane, cis-1-isocyano-4(2-isocyanopropyl)cyclohexane, 2,4-diisocyanopentane, 2-alkyl-1,3-diisocyanopropane, 1-isocyanobenzylisocyanamide, 1,2-diisocyanobenzene, 1,4-diisocyanocyclohexane, 1,8-diisocyanonaphthalene, 1,8-diisocyanofluorene, m-isocyanophenyl sulfone, 1,3-diisocyano-2,2,4,4-tetramethylcyclobutane, 1,3-diisocyano-2-hydroxy propane, 3,5-diisocyanobutane sulfonic acid or α,α'-diisocyano-o-xylene.
Claim 12
Dependent Claim
24 words
A reagent according to claim 10 in which the metal is rhodium and the biisocyanide is 1,3-diisocyanopropane and the Rhodium-rhodium separation is 3.26 A.
Claim 13
Dependent Claim
36 words
A reagent according to claim 2 in which the secondary oxidant is selected from the group consisting of cerium salts, molybdenum salts, iron +3 , copper +2 , quinones, permanganates, (IrCl 6 ) -2 or dichromates.
Claim 14
Dependent Claim
12 words
A reagent according to claim 13 further including a source of protons.
Claim 15
Independent Claim
54 words
A method of oxidizing a substrate comprising the steps of: adding the substrate to a solution containing a dimeric, dinuclear transition metal complex containing four binucleating diisocyanide bridge ligands and a secondary oxidant which is a stronger oxidizing agent than the complex; bubbling oxygen through the solution; and recovering oxidized substrate from the solution.
Claim 16
Independent Claim
54 words
A method of oxidizing a substrate comprising the steps of: adding the substrate to a solution containing a dimeric, dinuclear transition metal complex containing four binucleating diisocyanide bridge ligands and a secondary oxidant which is a stronger oxidizing agent than the complex; bubbling oxygen through the solution; and recovering oxidized substrate from the solution.
Claim 17
Dependent Claim
15 words
A method according to claim 14 in which the oxygen is bubbled through as air.
Claim 18
Dependent Claim
19 words
A method according to claim 15 in which the substrate is a gas and is bubbled through the solution.
Claim 19
Dependent Claim
31 words
A method according to claim 16 in which the solution is at a temperature from 0° C. to 150° C. and is maintained at a pressure from 1 to 20 atmospheres.
Claim 20
Dependent Claim
35 words
A method according to claim 17 in which the concentration of the complex is from 10 to 200 ppm and the secondary oxidant is present is stoichiometric excess based on metal content of the complex.
Claim 21
Dependent Claim
33 words
A method according to claim 18 in which the transition metal is selected from the platinum group and the binucleating biisocyanide contains 2 to 20 carbon atoms and the substrate is an olefin.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-06-01 | 1984-12-01 | 1985-06-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-06-01 | 1988-12-01 | 1989-06-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-06-01 | 1992-12-01 | 1993-06-02 | $7700.00 | Window Closed / Lapsed |