Oxygen exchange reactions of H/sub 2//sup 18/O with the hexacarbonyl cations of manganese and rhenium

Journal Article · Wed Jul 06 00:00:00 EDT 1977 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00456a033· OSTI ID:7218719

Darensbourg, D J; Froelich, J A

The reactions of (Mn(CO)/sub 6/)/sup +/ and (Re(CO)/sub 6/)/sup +/ with labeled water are described. The carbonyl ligands in these cationic carbonyl derivatives are found to undergo facile oxygen exchange reactions with H/sub 2//sup 18/O, presumably through a hydroxycarbonyl intermediate, (M(CO)/sub 5/C(O)OH), to afford (M(C/sup 16/O)/sub 6-n/(C/sup 18/O)/sub n/)/sup +/ s/species. In the manganese derivative ..beta..-hydrogen transfer in the intermediate is noted with the formation of oxygen-18 enriched HMn(C/sup 16/O)/sub 5-n/(C/sup 18/O)/sub n/ derivatives. The relative frequency for ..beta..-hydrogen transfer vs. oxygen exchange was found to be dependent on the nature of the metal center, with hydrogen transfer being retarded in the more electron-rich metal carbonyl centers such as (Mn(CO)/sub 5/L)/sup +/ (L = phosphine, pyridine, CH/sub 3/CN) and (Re(CO)/sub 6/)/sup +/.

• Research Organization: Tulane Univ., New Orleans
• OSTI ID: 7218719
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 99:14; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
CARBONYLS
COMPLEXES
EVEN-EVEN NUCLEI
HYDROGEN COMPOUNDS
ISOTOPES
ISOTOPIC EXCHANGE
LIGANDS
LIGHT NUCLEI
MANGANESE COMPLEXES
NUCLEI
OXYGEN 18
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
RHENIUM COMPLEXES
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
WATER