Biologically-Inspired Bimetallic Complexes for the Activation of Small Molecules

219 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2004.The activation of dihydrogen has only been observed indirectly through the photolytically-induced H/D exchange of [Fe2(mu-H)(SR) 2(CO)4(PR3)2]+ Fe-only hydrogenase models with D2. The diphosphine diruthenium complex Ru2(S2C3H6)(CO)4(PCy 3)2 oxidatively adds dihydrogen to produce the dihydride Ru2(S2C3H6)(mu-H)(H)(CO) 3(PCy3)2, the first example of the homolytic activation of dihydrogen by a synthetic Fe-only hydrogenase model. The protonation of the terminal hydride ligand of Ru2(S2C3H 6)(mu-H)(H)(CO)3(PCy3)2 has the potential to produce the first synthetic model of the Fe-only hydrogenase enzyme with a bound dihydrogen ligand. While these models are based on diruthenium systems rather than diiron systems, comparison of the iron-based enzyme to synthetic ruthenium mimics may lead to innovations in the preparation of biologically-inspired catalysts.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD