1H, 31P and 119Sn NMR studies of iridium trichlorostannate complexes

Abstract

The blue-green Ir(I) complexes resulting from the reaction of trans-[IrCl(CO)P 2], P = P(p-XC 6H 4) 3, X = H, F, Cl, OCH 3, with tin(II) chloride are discussed. The complexes are suggested to be isomers of composition [IrCl(CO)(SnCl 2)P 2] which contain bridging halogen ligands, and are unusual in that the tin is not coordinated to iridium. Reaction of a mixture of these intermediates with either HCl or H 2 gives the expected [IrHCl(SnCl 3)(CO)P 2] or [IrH 2(SnCl 3)(CO)P 2] products. These Ir(III) complexes contain the IrSn bond and show large 2J( 119Sn, 1H) trans coupling constants (>1200 Hz), which may be used to assign geometry. The products resulting from the reaction of Vaska's complex with tin(IV) chloride are suggested to be isomers involving five-coordinate tin and five-coordinate iridium. 119Sn, 31P NMR and 1H data for all the complexes are reported, with the metal chemical shift encompassing a range of ∼700 ppm. NMR spectroscopic data for the complexes [Ir(SnCl 3)(CO) 2P 2] and [Ir(O 2)(SnCl 3)CO(PPh 3) 2] are also reported.