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

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