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 = eta 5-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*Zr-2" (Cp* = eta(5)-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 degrees C, produces to a new rhodium thiolate complex [Rh(mu-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)(SC6K4NH)(COD) (7) by oxidative addition of the S-Me bond.