AMIDE COMPLEXES OF ZIRCONIUM, RHODIUM, AND IRIDIUM - SYNTHESIS AND REACTIVITY - X-RAY CRYSTAL-STRUCTURES OF (ETA(5)-C5H5)(2)ZR(NHC6H4-O-SME)(2) AND [RH(MU-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 Cp2 Zr(NHC6H4-o-SMe)(2) (2). The structure of 2 has been determined by X-r ay 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. R eaction of ''CpZr-2'' (Cp* = eta(5)-C5Me5) with 2-(methylmercapto)ani line yields a hydride-amide complex Cp2ZrH(NHC6H4) (4). Reaction of c omplex 2 with [RhCl(COD)](2) generates complex 3 and the new rhodium a mide complex Rh(NHC6H4-o-SMe)(COD), which has been also directly synth esized by reacting [RhCl(COD)](2) with LiNHC6H4-o-SMe. Thermolysis of complex 6, at 100 degrees C, produces to a new rhodium thiolate comple x [Rh(mu-SC6H4-o-NHMe)-(COD)](2) (5). Its structure has been determine d by X-ray diffraction methods. Reaction of [IrCl(COD)](2) with LiNHC6 H4-o-SMe gives the iridium(III) complex Ir(Me)(SC6K4NH)(COD) (7) by ox idative addition of the S-Me bond.