Synthesis and Reactivity of Iridium(I) Fluorido Complexes: Oxidative Addition of SF 4 at trans ‐[Ir(F)(CO)(PEt 3 ) 2 ]

The facile access to the Vaska type fluorido complexes trans ‐[Ir(F)(CO)(PR 3 ) 2 ] [ 6 : R = Et, 7 : R = Ph, 8 : R = i Pr, 9 : R = Cy, 10 : R = t Bu] was achieved by halide exchange at trans ‐[Ir(Cl)(CO)(PR 3 ) 2 ] ( 1 – 5 ) with Me 4 NF. Furthermore, the reaction of complex 6 with SF 4 gave cis,trans ‐[Ir(F) 2 (SF 3 )(CO)(PEt 3 ) 2 ] ( 11 ), whereas 8 – 10 did not react. Reactivity studies revealed that 11 can selectively be manipulated at the sulfur atom by hydrolysis or fluoride abstraction to give cis,trans ‐[Ir(F) 2 (SOF)(CO)(PEt 3 ) 2 ] ( 12 ) and cis,trans ‐[Ir(F) 2 (SF 2 )(CO)(PEt 3 ) 2 ][AsF 6 ] ( 13 ), respectively.