Novel triaikylstlbane iridium(I) and iridium(III) complexes including the X-ray crystal structure of five-coordinate [IrCl(C2H4)2(SbiPr3)2]

Article abstract of DOI:10.1002/cber.19961290409

The reaction of [IrCl(C₈H₁₄)₂]₂ (2) with SbiPr₃ in the presence of H₂ yields the dihydridoiridium(III) complex cis,mer[IrH₂Cl(SbiPr₃)₃] (3) which on treatment with CO and with HC≡CR (R = Ph, CO₂Me) affords the octahedral derivatives [IrH₂Cl(CO)(SbiPr₃)₂] (4) and [IrHCl(C=CR)(SbiPr₃)₃] (5, 6), respectively. The stibane ligand trans to hydride in 5 and 6 is rather labile and, therefore, 5 and 6 react with pyridine to give [IrHCl(C=CR)(py)(SbiPr₃))₂] (7, 8). Five-coordinate bis-(stibane)iridium(I) complexes [IrCl(C₂H₄)₂(SbR₃)₂] (10-12) were prepared from [IrCl(C₂H₄)₂]₂ (9) and four equiv. of SbR₃ (R = iPr, Me, Ph). The X-ray crystal structural analysis of 10 reveals a distorted trigonal-bipyramidal geometry around the metal center with one stibane ligand and the two olefinic ligands in the equatorial plane. Compound 10 reacts with NaC₅H₅ to yield [C₅H₅Ir(C₂H₄)(SbiPr₃)] (13) and with different alkynes by partial or complete displacement of the ethene ligands to give trans-[IrCl(PhC≡CPh)(SbiPr₃)₂] (14), [IrHCl(C≡CTol)(C₂H₄)(SbiPr₃)₂] (15), and trans-[IrCl-{ = C = C(SiMe₃)R}(SbiPr₃)₂] (16, 17), respectively. VCH Verlagsgescllschaft mbH 1996.