Claims
- 1. A photoreduction process comprising the steps of:
- (a) irradiating (M.sub.2 (Bridge).sub.4)X.sub.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.sub.2 (Bridge).sub.4 X.sub.2).sup.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).
- 2. A method in accordance with claim 1 in which the transition metal is a platinum group metal.
- 3. A method according to claim 2 in which the metal is selected from rhodium, cobalt, iridium, platinum, palladium, nickel, osmium, ruthenium or iron.
- 4. A method according to claim 3 in which the dinucleating diisocyanide is selected from compounds of the formula (CN).sub.2 R where R is an organic divalent group containing 2 to 20 carbon atoms.
- 5. A method according to claim 4 in which X is selected from halo, tetraphenyl borate, PF.sub.6.sup.- or boron tetrafluoride.
- 6. A method according to claim 5 in which R is selected from alkylene, arylene, alkarylene, cycloalkylene, alkylcyoalkylene or alkarylene.
- 7. 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 .alpha.,.alpha.'-diisocyano-m-xylene.
- 8. 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.
- 9. A method according to claim 1 in which the irradiation includes light having wavelength between 500 and 600 nm.
- 10. A method according to claim 9 in which the substrate is water and the anion is halo.
- 11. 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.
- 12. A method according to claim 11 in which the hydrohalic acid is HBr.
- 13. A method according to claim 1 in which the oxidizable substrate is an olefin.
- 14. A method according to claim 13 in which the olefin is selected from ethylene, or propylene.
- 15. A method according to claim 1 in which the oxidizable substrate is methanol or acetylene.
ORIGIN OF THE INVENTION
The Government has rights in this invention pursuant to Grant #CHE77-11389 awarded by the National Science Foundation.
US Referenced Citations (1)
Number |
Name |
Date |
Kind |
3154586 |
Bander et al. |
Oct 1964 |
|
Non-Patent Literature Citations (1)
Entry |
C & E N (Aug. 1, 1977), pp. 15 & 16. |