Synthesis, Structure and Reactivity of Iridium Hydrido Fluorido Complexes

The oxidative addition of HF at trans ‐[Ir(Ar F )(η 2 ‐C 2 H 4 )(P i Pr 3 ) 2 ] ( 1a : Ar F = 4‐C 5 NF 4 ; 1b : Ar F = 2‐C 6 H 3 F 2 ) affords the fluorido complexes trans ‐[Ir(Ar F )(F)(H)(P i Pr 3 ) 2 ] ( 2a : Ar F = 4‐C 5 NF 4 ; 2b : Ar F = 2‐C 6 H 3 F 2 ). The hydrido fluorido complex 2a is also accessible by means of the reaction of the hydroxido complex trans ‐[Ir(4‐C 5 NF 4 )(H)(OH)(P i Pr 3 ) 2 ] ( 3a ) with Et 3 N · 3HF. Both compounds 2a and 2b react with CO to give the carbonyl complexes trans ‐[Ir(4‐C 5 NF 4 )(F)(H)(CO)(P i Pr 3 ) 2 ] ( 4a : Ar F = 4‐C 5 NF 4 ; 4b : Ar F = 2‐C 6 H 3 F 2 ). In the presence of traces of water, a slow reaction of 2a with CO 2 yields the hydrogencarbonato complex trans ‐[Ir(4‐C 5 NF 4 )(H)(κ 2 ‐( O , O )‐ O 2 COH)(P i Pr 3 ) 2 ] ( 5a ). Upon using 2a or 2b as fluorinating agent, Ph 3 SiH could be converted into Ph 3 SiF and CH 3 C(O)Cl into CH 3 C(O)F.