Oxygen exchange reactions of water (oxygen-18) with hexacarbonyl cations of manganese and rhenium Academic Article uri icon


  • The reactions of [Mn(CO)6]+ and [Re(CO)6]+ with labeled water are described. The carbonyl ligands in these cationic carbonyl derivatives are found to undergo facile oxygen exchange reactions with H218O, presumably through a hydroxy-carbonyl intermediate, [M(CO)sC(0)OH], to afford [M(C6O)6-μ(C18O)n]+ species. In the manganese derivative (3-hydrogen transfer in the intermediate is noted with the formation of oxygen-18 enriched HMn(Cl6O)5s_n(Cl8O)n derivatives. The relative frequency for β-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)5L]+ (L = phosphine, pyridine, CH3CN) and [Re(CO)6] +. © 1977, American Chemical Society. All rights reserved.

author list (cited authors)

  • Darensbourg, D. J., & Froelich, J. A

complete list of authors

  • Darensbourg, Donald J||Froelich, Joseph A

publication date

  • January 1, 1977 11:11 AM