Reactions of rhodium(II) and iridium(III) complexes bearing a P,O-coordination with tetracyanoethylene in the presence of KPF 6

Abstract

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