US4169030A
Expired / Lapsed
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Light assisted reactions of dinuclear diisocyano ligand bridged complexes
Assignee: California Institute of Technology
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Filing: 1978-08-03
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Granted: 1979-09-25
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Expires: 1998-08-03
Abstract
Abstract A complex ion containing rhodium, Rh2(1,3-diisocyanopropane)42+ is called "rhodium bridge." Because of the nature of its molecular structure, it is deep blue in water solution. Irradiation of the blue complex between 500 and 600 nm leads to direct reduction of the protons in water to hydrogen gas. In this reaction rhodium bridge is converted to a yellow form, in which each of the two rhodiums has lost one electron. The H2-producing visible photoreaction of rhodium bridge can be utilized in a solar-driven water splitting cycle.
Inventors
- 👤 Harry B. Gray
- 👤 Kent Mann
- 👤 Nathan Lewis
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 00:02
CPC Classifications
C; C01; C01B; C01B3/00; C01B3/02; C01B3/04; C01B3/042; B; B01; B01J; B01J19/00; B01J19/08; B01J19/12; B01J19/122; B01J19/127; Y; Y02; Y02E; Y02E60/00; Y02E60/30; Y02E60/36
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
124 words
A photoreduction process comprising the steps of: (a) irradiating (M 2 (Bridge) 4 )X 2 reductant with visible light in the presence of substrate where M is a transition metal, Bridge is a dinnucleating diisocyanide and X is an anion to form an excited state of the reductant; (b) reducing the substrate with the excited reductant and generating a higher oxidized state of the reductant of the formula; (M 2 (Bridge) 4 X 2 ) 2+ ; (c) separating the reduced substrate from the oxidized reductant; (d) combining the oxidized reductant with an oxidizable substrate; (e) oxidizing the oxidizable substrate while reducing the oxidized reductant to said reductant form; and (f) separating the reductant from oxidized substrate and recycling the reductant to step (a).
Claim 2
Dependent Claim
124 words
A photoreduction process comprising the steps of: (a) irradiating (M 2 (Bridge) 4 )X 2 reductant with visible light in the presence of substrate where M is a transition metal, Bridge is a dinnucleating diisocyanide and X is an anion to form an excited state of the reductant; (b) reducing the substrate with the excited reductant and generating a higher oxidized state of the reductant of the formula; (M 2 (Bridge) 4 X 2 ) 2+ ; (c) separating the reduced substrate from the oxidized reductant; (d) combining the oxidized reductant with an oxidizable substrate; (e) oxidizing the oxidizable substrate while reducing the oxidized reductant to said reductant form; and (f) separating the reductant from oxidized substrate and recycling the reductant to step (a).
Claim 3
Dependent Claim
17 words
A method in accordance with claim 1 in which the transition metal is a platinum group metal.
Claim 4
Dependent Claim
23 words
A method according to claim 2 in which the metal is selected from rhodium, cobalt, iridium, platinum, palladium, nickel, osmium, ruthenium or iron.
Claim 5
Dependent Claim
34 words
A method according to claim 3 in which the dinucleating diisocyanide is selected from compounds of the formula (CN) 2 R where R is an organic divalent group containing 2 to 20 carbon atoms.
Claim 6
Dependent Claim
21 words
A method according to claim 4 in which X is selected from halo, tetraphenyl borate, PF 6 - or boron tetrafluoride.
Claim 7
Dependent Claim
19 words
A method according to claim 5 in which R is selected from alkylene, arylene, alkarylene, cycloalkylene, alkylcyoalkylene or alkarylene.
Claim 8
Dependent Claim
34 words
A method according to claim 5 in which the diisocyanide 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, 2,4-diisocyanobutane sulfonic acid or α,α'-diisocyano-m-xylene.
Claim 9
Dependent Claim
23 words
A method according to claim 7 in which the metal is rhodium and the diisocyanide is 1,3-diisocyanopropane and the rhodium-rhodium separation is 3.26A.
Claim 10
Dependent Claim
19 words
A method according to claim 1 in which the irradiation includes light having wavelength between 500 and 600 nm.
Claim 11
Dependent Claim
17 words
A method according to claim 9 in which the substrate is water and the anion is halo.
Claim 12
Dependent Claim
28 words
A method according to claim 10 in which the water contains hydrohalic acid at a molarity above 8 and molecular hydrogen gas is produced during the photoreduction reaction.
Claim 13
Dependent Claim
13 words
A method according to claim 11 in which the hydrohalic acid is HBr.
Claim 14
Dependent Claim
14 words
A method according to claim 1 in which the oxidizable substrate is an olefin.
Claim 15
Dependent Claim
16 words
A method according to claim 13 in which the olefin is selected from ethylene, or propylene.
Claim 16
Dependent Claim
15 words
A method according to claim 1 in which the oxidizable substrate is methanol or acetylene.
References Cited (Backward Citations)
US3154586A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1982-09-24 | 1983-03-26 | 1983-09-25 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-09-24 | 1987-03-26 | 1987-09-25 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-09-24 | 1991-03-26 | 1991-09-25 | $7700.00 | Window Closed / Lapsed |