Chemical and infrared spectral details of reactions involving stereospecific incorporation of oxygen-18 into substituted manganese and rhenium carbonyl derivatives via exchange reactions with H/sub 2//sup 18/O

Journal Article · Wed Aug 31 00:00:00 EDT 1977 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00460a017· OSTI ID:7210500

Darensbourg, D J; Froelich, J A

The reactions of substituted group 7B metal carbonyl cationic derivatives, (M(CO)/sub 5/L)/sup +/ (M = Mn, Re and L = phosphine, C/sub 5/H/sub 5/N, CH/sub 3/CN) and (Mn(CO)/sub 4/(diphos))/sup +/, with labeled water are described. The carbonyl ligands in these derivatives are found to undergo facile oxygen-exchange reactions with H/sub 2//sup 18/O, presumably through hydroxycarbonyl intermediates, to afford C/sup 18/O enriched species. In all cases investigated, the carbonyl sites with the higher CO stretching force constant (implying more positive character at carbon as well as a more stable LUMO) were found to be more susceptible to oxygen exchange, thus leading to stereospecifically labeled species. In addition, the reactivity of the substrate toward oxygen exchange with water was found to decrease in the order (M(CO)/sub 6/)/sup +/ > (M(CO)/sub 5/L)/sup +/ >> (M(CO)/sub 4/(L - L))/sup +/. The preparation of cis-(Mn(CO)/sub 4/(/sup 13/CO)L)/sup +/ (L = PMe/sub 2/Ph, PPh/sub 3/, and AsPh/sub 3/) species is reported along with oxygen-18 exchange reactions of these derivatives to yield mixed labeled (/sup 13/C/sup 18/O) metal carbonyls. The incorporation of oxygen-18 into metal carbonyl cations was found to be greatly accelerated by the addition of small quantities of triethylamine.

• Research Organization: Tulane Univ., New Orleans
• OSTI ID: 7210500
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 99:18; 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)
AQUEOUS SOLUTIONS
CARBONYLS
CHEMICAL REACTION KINETICS
DISPERSIONS
EVEN-EVEN NUCLEI
INFRARED SPECTRA
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
MANGANESE COMPOUNDS
MIXTURES
NUCLEI
OXYGEN 18
OXYGEN ISOTOPES
REACTION KINETICS
RHENIUM COMPOUNDS
SOLUTIONS
SPECTRA
STABLE ISOTOPES
STEREOCHEMISTRY
TRANSITION ELEMENT COMPOUNDS