Synthesis and Reactivity of Ir(I) and Ir(III) Complexes with MeNH2, Me2CNR (R = H, Me), C,N-C6H4{C(Me)N(Me)}-2, and N,N′
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- 作者：José ; Vicente ; Marí ; a Teresa Chicote ; Inmaculada Vicente-Herná ; ndez ; Delia Bautista
- 刊名：Inorganic Chemistry
- 出版年：2008
- 出版时间：October 20, 2008
- 年：2008
- 卷：47
- 期：20
- 页码：9592-9605
- 全文大小：411K
- 年卷期：v.47,no.20(October 20, 2008)
- ISSN：1520-510X
文摘
Complexes [Ir(Cp*)Cln(NH2Me)3−n]Xm (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(μ-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 = ClO4) is obtained from 2a and NaClO4·H2O. The reaction of 3 with MeC(O)Ph at 80 °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 = tBu (5), Xy (6)). [Ir(μ-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(NHCMe2)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(μ-Cl)]2 reacts with [Au(NHCMe2)(PPh3)]ClO4 (1:2) to give [Ir(Cp*)(μ-Cl)(NHCMe2)]2(ClO4)2 (12) which in turn reacts with PPh3 or Me4NCl (1:2) to give [Ir(Cp*)Cl(NHCMe2)(PPh3)]ClO4 (13) or [Ir(Cp*)Cl2(NHCMe2)] (14), respectively. Complex 14 hydrolyzes in a CH2Cl2/Et2O solution to give [Ir(Cp*)Cl2(NH3)] (15). The reaction of [Ir(Cp*)Cl(μ-Cl)]2 with [Ag(NHCMe2)2]ClO4 (1:4) gives [Ir(Cp*)(NHCMe2)3](ClO4)2 (16a), which reacts with PPNCl (PPN = Ph3PNPPh3) under different reaction conditions to give [Ir(Cp*)(NHCMe2)3]XY (X = Cl, Y = ClO4 (16b); X = Y = Cl (16c)). Equimolar amounts of 14 and 16a react to give [Ir(Cp*)Cl(NHCMe2)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(NHCMe2)2]ClO4 to give [Ir(Cp*)(R-imam)L](ClO4)2 (R = H, L = tBuNC (20), XyNC (21); R = Me, L = MeCN (22)) or [Ir(Cp*)(H-imam)(NHCMe2)](ClO4)2 (23a), respectively. The later reacts with PPNCl to give [Ir(Cp*)(H-imam)(NHCMe2)]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.