Reactions involving transition metals. Part 15. Reactions of alkyl- and acyl-peroxy-anions with [M(CO)(MeCN)(PPh3)2]+(M = Ir or Rh)

Abstract

The title compounds react with peroxycarboxylic acids RCO₃H in the presence of NEt₃ to give the compounds [M(O₂CR)(CO)L₂](L = PPh₃), which, with Mel, give [IrMe(I)(OCOC₆H₄Cl-m)(CO)L₂] and [Rhl(O₂CR)(COMe)L₂](R = C₆H₄Cl-m, Ph, or Me). Reaction between NaO₂COR′(R′= C₆H₄Cl-m) and [Ir(CO)(MeCN)L₂]⁺ affords an inseparable mixture of [Ir(O₂CR′)(CO)L₂], [Ir(O₂)(O₂CR′)(CO)L₂], [Ir(O₃CR′)(CO)L₂], and [Ir(O₂)(O₃CR′)(CO)L₂]; under similar conditions the rhodium analogue gives a mixture of [Rh(O₂CR′)(CO)L₂]. Reactions between NaO₂Bu^t and either [Ir(CO)(MeCN)L₂]⁺ or [IrF(CO)L₂] give only [Ir(OH)(CO)L₂].