Amide Complexes of Zirconium, Rhodium, and Iridium:  Synthesis and Reactivity. X-ray Crystal Structures of (η⁵-C₅H₅)₂Zr(NHC₆H₄-o-SMe)₂ and [Rh(μ-SC₆H₄-o-NHMe)(COD)]₂^†

The reaction of Cp₂ZrCl₂ (Cp = η⁵-C₅H₅) with 2 equiv of the lithium amide derivative LiNHC₆H₄-o-SMe affords the new zirconium complex Cp₂Zr(NHC₆H₄-o-SMe)₂ (2). The structure of 2 has been determined by X-ray diffraction. When the reaction is carried out in an 1:1 ratio, the complex Cp₂ZrCl(NHC₆H₄-o-SMe) (3) is generated as the major product. Reaction of “Cp*₂Zr” (Cp* = η⁵-C₅Me₅) with 2-(methylmercapto)aniline yields a hydride−amide complex Cp*₂ZrH(NHC₆H₄) (4). Reaction of complex 2 with [RhCl(COD)]₂ generates complex 3 and the new rhodium amide complex Rh(NHC₆H₄-o-SMe)(COD), which has been also directly synthesized by reacting [RhCl(COD)]₂ with LiNHC₆H₄-o-SMe. Thermolysis of complex 6, at 100 °C, produces to a new rhodium thiolate complex [Rh(μ-SC₆H₄-o-NHMe)(COD)]₂ (5). Its structure has been determined by X-ray diffraction methods. Reaction of [IrCl(COD)]₂ with LiNHC₆H₄-o-SMe gives the iridium(III) complex Ir(Me)(SC₆H₄NH)(COD) (7) by oxidative addition of the S−Me bond.