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Part I: the electrocatalytic reduction of carbon dioxide using macrocycles of nickel and cobalt. Part II: the preparation, characterization and reaction chemistry of some new iridium bis(tertiary phosphine) complexes

Thesis/Dissertation ·
OSTI ID:5616862
The iridium(III) hydride adducts of these complexes were prepared. Binuclear dppp (1,3-bis-diphenylphosphino)-propane) bridged complexes of formula (IrH/sub 2/X(CO)(dppp))/sub 2/ where X = Br, I, possess the phosphine donors in trans positions. Upon heating, these dimers cleave into monomeric species of the same stoichiometry. The dppe (1,2-bis(diphenylphosphine)ethane) complexes are all mononuclear and contain a chelated ligand. The new complexes IrX(CO)(dppe) where X = Br, I, have been described, as has their reaction chemistry to form reversible adducts with CO and H/sub 2/. The trihydride complex IrH/sub 3/(C)(dppe) has been prepared. Under irradiation or heating, H/sub 2/ is eliminated, yielding IrD/sub 3/(CO(dppe) under D/sub 2/ and IrH(CO)2(dppe) under CO. In C/sub 6/D/sub 6/ under vacuum, IrH/sub 3/(CO)(dppe) shows evidence of H/D exchange only upon irradiation, indicating arene C-H bond activation involving a photochemical process. When irradiation of IrH/sub 3/(CO(dppe) In C/sub 6/H/sub 6/ under CO is carried out, benzaldehyde is produced. One important secondary reaction upon prolonged photolysis is the subsequent conversion of benzaldehyde to benzyl alcohol.
OSTI ID:
5616862
Country of Publication:
United States
Language:
English