Reactions of niterogen mono-oxide and nitrogen dioxde with methylplatinum and methylgold complexes

Abstract

Nitrogen mono-oxide reacts with cis-[PtMe₂(PMe₂Ph)₂] to give first cis-cis-cis-[PtMe₂(NO₂)₂(PMe₂Ph)₂] which then isomerises to the more stable cis-cis-trans isomer. The final products, however, are trans-[PtMe(NO₂)(PMe₂Ph)₂] and fac-[PtMe₃(NO₂)(PMe₂Ph)₂] formed by reaction of cis-[PtMe₂(PMe₂Ph)₂] with [PtMe₂(NO₂)₂(PMe₂Ph)₂]. Nitrogen dioxide reacts with cis-[PtMe₂(PMe₂Ph)₂] to give cis-cis-trans-[PtMe₂(NO₃)₂(PMe₂Ph)₂], while both NO and NO₂, react with [AuMe₃(PMe₂Ph)] to give cis-[AuMe₂(NO₂)(PMe₂Ph)]. Nitrogen monooxide reacts with trans-[PtHI(PMe₂Ph)₂] to give cis-[PtI (NO₂)(PMe₂Ph)₂]. which is also formed in the symmetrisation reaction between cis-[Pt(NO₂)₂(PMe₂Ph)₂] and [PtI₂(PMe₂Ph₂)]. Possible mechanisms of reaction are discussed.