Complexes of Iridium and Platinum Containing 5-Coordinated Phosphorus

Abstract
The complex Ir(CO)Cl2(PEt3)2(P′F4), prepared in high yield from Ir(CO)Cl2(PEt3)2(P′F2) and XeF2, has been characterised by nmr spectroscopy, by analysis and by X-ray crystallography. In the crystal, P′ is trans to Cl, and is trigonal-bipyramidal, with Ir in an equatorial position and the P′F bonds staggered with respect to the octahedral coordination round Ir. In solution, the fluxional behaviour of P′ is only slowed enough to resolve distinct F resonances at 135 K. NMR evidences indicates that XeF2 reacts at 180 K with Ir(CO)BrH(PEt3)2(P′H2) to give Ir(CO)BrH(PEt3)2(P′F2H2), which is unstable at 210 K. XeF2 also reacts with PtCl(PEt3)2(P′Cl2) to give PtCl2(PEt3)2(P′F4), not yet isolated; in this complex P′ is fluxional at 280 K but distinct F resonances are observed at 180 K.

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