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Catalytic Hydration of Alkenes and Alkynes [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy. Office of Energy Research, 2003.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Additional Creators
University of Buffalo, United States. Department of Energy. Office of Energy Research, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
The fifteen years of DOE support have encompassed two different projects, electron-transfer reactions of metal carbonyl anions and water-soluble organometallic complexes. Each of these is related to homogeneous catalysis and will be described in separate sections. Electron Transfer--Twenty-one manuscripts resulted from our studies of electron-transfer reactions of metal carbonyl anions and acknowledge DOE support. Construction of an infrared stopped-flow system allowed us to measure rates of reactions for the extremely air-sensitive metal carbonyl anions. As for carbanions, both one-electron and two-electron processes occur for metal carbonyl anions. The most unexpected feature was examples of a very rapid two-electron process, followed by a much slower one-electron back transfer. The two-electron processes were accompanied by transfer of a ligand between two metals, M-X + M′⁻ → M⁻ + M′-X with X groups of CO², H⁺, CH₃⁺ and Br⁺. These transfers, which can be considered nucleophilic displacements, occurred when M′⁻ was more nucleophilic than M⁻. The 21 published manuscripts explore one- and two-electron processes for many such organometallic complexes. Water-Soluble Organometallic Complexes--The potential of water-soluble organometallic complexes in ''green chemistry'' intrigued us. Sixteen manuscripts acknowledging DOE support have appeared thus far in this field. Our research centered on sulfonated phosphine ligands, PPh₂(m-C₆H₄SO₃Na) and P(m-C₆H₄SO₃Na)₃, to solubilize organometallic complexes in water. These analogues of PPH₃ allowed us to synthesize complexes of Ir, Rh, Ru, Ni, Pd, Pt and Ag that are water-soluble and contain such common organometallic ligands as CO, H and CH₃ in addition to halides and the phosphine ligands. These metal complexes show the ability to activate H₂, CO, C₂H₄, H₂O, SO₂ etc. in aqueous solution. The primary conclusion is that water-soluble organometallic complexes can be prepared and show very similar reactivity in water to analogous compounds in organic solvents. Thus, organometallic complexes in aqueous solution do provide a ''green'' route to products currently prepared in organic solvents.
Report Numbers
E 1.99:808955
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Note
Published through SciTech Connect.
03/18/2003.
Atwood, Jim, D.
Type of Report and Period Covered Note
Final; 01/01/1987 - 12/31/2002
Funding Information
FG02-87ER13775
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