Reactions of rhodium(II) and iridium(III) complexes bearing a P,O-coordination with tetracyanoethylene in the presence of KPF6 |
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Authors: | Yasuhiro Yamamoto Asako Takahashi Kazuyuki Tatsumi |
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Affiliation: | a Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan b Research Center for Materials Science and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 454-8602, Japan |
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Abstract: | 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. |
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Keywords: | Tetracyanoethylene Pentamethylcyclopentadienyl Rhodium(III) Iridium(III) C-CN bond cleavage |
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