Synthesis, Structure and Reactivity of Iridium Hydrido Fluorido Complexes

The oxidative addition of HF at trans-[Ir(ArF)(η2-C2H4)(PiPr3)2] (1a: ArF = 4-C5NF4; 1b: ArF = 2-C6H3F2) affords the fluorido complexes trans-[Ir(ArF)(F)(H)(PiPr3)2] (2a: ArF = 4-C5NF4; 2b: ArF = 2-C6H3F2). The hydrido fluorido complex 2a is also accessible by means of the reaction of the hydroxido complex trans-[Ir(4-C5NF4)(H)(OH)(PiPr3)2] (3a) with Et3N·3HF. Both compounds 2a and 2b react with CO to give the carbonyl complexes trans-[Ir(4-C5NF4)(F)(H)(CO)(PiPr3)2] (4a: ArF = 4-C5NF4; 4b: ArF = 2-C6H3F2). In the presence of traces of water, a slow reaction of 2a with CO2 yields the hydrogencarbonato complex trans-[Ir(4-C5NF4)(H)(κ2-(O,O)-O2COH)(PiPr3)2] (5a). Upon using 2a or 2b as fluorinating agent, Ph3SiH could be converted into Ph3SiF and CH3C(O)Cl into CH3C(O)F.