Type of Document	Dissertation
Author	Le, Trang X.
URN	etd-09232008-144717
Title	Oxidation addition of H-H bonds to iridium :developing novel active water soluble catalysts for hydrogenation of unsaturates
Degree	PhD
Department	Chemistry
Advisory Committee	Advisor Name Title No Advisors Found
Keywords	Oxidizing agents
Date of Defense	1992-08-05
Availability	restricted
Abstract The oxidative addition of H-H to iridium(l) trimethylphosphine complexes was studied and the reactivity of the resulting water soluble dihydrido iridium (III) complexes was investigated. One Dihydrido iridium(III) complex, mer-Ir(H)2(PMe3)3CI (2) was characterized by IH, 31p and 13C NMR spectroscopy, CH analysis and single crystal xray diffraction. (2) reacted with the strong sigma donor PMe3 to form [IrH2(PMe3)4]CI (3b) without having to remove the chloride ligand. (2) reacted with monosubstituted acetylenes and an internal diyne in water to form the vinyl complexes Ir(H)(C(R')=C(H)( R»(PMe3)3CI (R = CMe3, C6lis, SiMe3, R' = H, (4)-(6); R' = CCMe3, R= Me, (7». (2) also reacted in water with ethynylpyridine to form an unusual metallacycle "trimer" (8). A mechanism for tltrimerizationtl is proposed. (2) also reacted with ethylene in water to form the diethyl iridium complex Ir(CH2CH3)2(PMe3)3CI (8). Encouraged by these results, catalytic hydrogenation of unsaturates in water was investigated. It was found that (2) is active as a water soluble catalyst for hydrogenation of unsaturates. A mechanism for catalytic hydrogenation was proposed.
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