Reactions of rhodium(II) and iridium(III) complexes bearing a P,O-coordination with tetracyanoethylene in the presence of KPF6

Reactions of Cp*M(MDMPP-P,O)Cl (1a: M=Rh, 1b: M=Ir; MDMPP-P,O=PPh2(2-O-6-MeOC6H3)) with tetracyanoethylene (tcne) in the presence of KPF6 gave Cp*MCl[PPh2{2-O-3-(C(CN)2CH(CN)2)-6-MeOC6H2}] (2), [{Cp*MPPh2{2-O-3-(C(CN)C(CN)2)-6-MeOC6H2}}2(CN)](PF6) (3), [{Cp*IrPPh2{2-O-3-(C(CN)C(CN)2)-6-MeOC6H2}}(CN){Cp*Ir(MDMPP-P,O)}](PF6) (4b) and [{Cp*Ir(MDMPP-P,O)}2(CN)](PF6) (5b), depending on the reaction conditions. Reaction of 2 with KPF6 or AgOTf in the absence and presence of xylyl isocyanide (XylNC) gave 3 or [Cp*MCl{PPh2(2-O-3-(C(CN)2-CH(CN)2)-6-MeOC6H2)}(XylNC)](OTf) (6). The structure of 3a (M=Rh) was confirmed by X-ray crystal analysis.