Synthesis and reactivity of Ir(I) and Ir(III) complexes with MeNH2, Me2C=NR (R = H, Me), C,N-C6H4{C(Me)=N(Me)}-2, and N,N'-RN=C(Me)CH2C(Me2)NHR (R = H, Me) ligands

Complexes Ir(Cp*)Cl(n)(NH2Me)(3-n)]X(m) (n = 2, m = 0 (1), n = 1, m = 1, X = Cl (2a), n = 0, m = 2, X = OTf (3)) are obtained by reacting Ir(Cp*)Cl(mu-Cl)]2 with MeNH2 (1:2 or 1:8) or with Ag(NH2Me)2]OTf (1:4), respectively. Complex 2b (n = 1, m = 1, X = ClO 4) is obtained from 2a and NaClO4 x H2O. The reaction of 3 with MeC(O)Ph at 80 degrees C gives Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(NH2Me)]OTf (4), which in turn reacts with RNC to give Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(CNR)]OTf (R = (t)Bu (5), Xy (6)). Ir(mu-Cl)(COD)]2 reacts with Ag{N(R)=CMe2}2]X (1:2) to give Ir{N(R)=CMe2}2(COD)]X (R = H, X = ClO4 (7); R = Me, X = OTf (8)). Complexes Ir(CO)2(NH=CMe2)2]ClO4 (9) and IrCl{N(R)=CMe2}(COD)] (R = H (10), Me (11)) are obtained from the appropriate Ir{N(R)=CMe2}2(COD)]X and CO or Me4NCl, respectively. Ir(Cp*)Cl(mu-Cl)]2 reacts with Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give Ir(Cp*)(mu-Cl)(NH=CMe2)]2(ClO4)2 (12) which in turn reacts with PPh 3 or Me4NCl (1:2) to give Ir(Cp*)Cl(NH=CMe2)(PPh3)]ClO4 (13) or Ir(Cp*)Cl2(NH=CMe2)] (14), respectively. Complex 14 hydrolyzes in a CH2Cl2/Et2O solution to give Ir(Cp*)Cl2(NH3)] (15). The reaction of Ir(Cp*)Cl(mu-Cl)]2 with Ag(NH=CMe2)2]ClO4 (1:4) gives Ir(Cp*)(NH=CMe2)3](ClO4)2 (16a), which reacts with PPNCl (PPN = Ph3=P=N=PPh3) under different reaction conditions to give Ir(Cp*)(NH=CMe2)3]XY (X = Cl, Y = ClO4 (16b); X = Y = Cl (16c)). Equimolar amounts of 14 and 16a react to give Ir(Cp*)Cl(NH=CMe2)2]ClO4 (17), which in turn reacts with PPNCl to give Ir(Cp*)Cl(H-imam)]Cl (R-imam = N,N'-N(R)=C(Me)CH2C(Me)2NHR (18a)]. Complexes Ir(Cp*)Cl(R-imam)]ClO4 (R = H (18b), Me (19)) are obtained from 18a and AgClO4 or by refluxing 2b in acetone for 7 h, respectively. They react with AgClO4 and the appropriate neutral ligand or with Ag(NH=CMe2)2]ClO4 to give Ir(Cp*)(R-imam)L](ClO4)2 (R = H, L = (t)BuNC (20), XyNC (21); R = Me, L = MeCN (22)) or Ir(Cp*)(H-imam)(NH=CMe2)](ClO4)2 (23a), respectively. The later reacts with PPNCl to give Ir(Cp*)(H-imam)(NH=CMe2)]Cl(ClO4) (23b). The reaction of 22 with XyNC gives Ir(Cp*)(Me-imam)(CNXy)](ClO4)2 (24). The structures of complexes 15, 16c and 18b have been solved by X-ray diffraction methods.