Synthesis, Reactivity and Structures of Iridium Tetrafluoropyridyl Complexes: Ammonia Coordination and Activation

Abstract. The complex cis ‐ trans ‐[Ir(4‐C 5 NF 4 )(H) 2 (P i Pr 3 ) 2 ] ( 1 ) reacted with ammonia to give cis ‐ trans ‐[Ir(4‐C 5 NF 4 )(H) 2 (NH 3 )(P i Pr 3 ) 2 ] ( 2a ). The reaction of 1 with ND 3 yielded the isotopomer cis ‐ trans ‐[Ir(4‐C 5 NF 4 )(H) 2 (ND 3 )(P i Pr 3 ) 2 ] ( 2b ). Within two weeks hydrido ligands were replaced by metal bound deuterium atoms via H/D exchange. Treatment of trans ‐[Ir(4‐C 5 NF 4 )(η 2 ‐C 2 H 4 )(P i Pr 3 ) 2 ] ( 3 ) with HCl led to the formation of trans ‐[Ir(4‐C 5 NF 4 )(Cl)(H)(P i Pr 3 ) 2 ] ( 4 ). Complex 4 reacted with CO or ammonia to give trans ‐[Ir(4‐C 5 NF 4 )(Cl)(H)(CO)(P i Pr 3 ) 2 ] ( 5 ) and the ammine complex trans ‐[Ir(4‐C 5 NF 4 )(Cl)(H)(NH 3 )(P i Pr 3 ) 2 ] ( 6a ), respectively. The cationic species [(η 6 ‐C 6 H 6 )Ir(H) 2 (P i Pr 3 )][PF 6 ] ( 7 ) was obtained by reaction of cis ‐ trans ‐[Ir(4‐C 5 NF 4 )(H) 2 (NH 3 )(P i Pr 3 ) 2 ] ( 2a ) or cis ‐ trans ‐[Ir(4‐C 5 NF 4 )(H) 2 (P i Pr 3 ) 2 ] ( 1 ) with [Ph 3 C][PF 6 ] in benzene.