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

Article abstract of DOI:10.1016/j.ica.2004.04.014

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)](PF ₆) (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)](PF ₆) (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.