The First Acetimino Complexes of Rh(III). 4-Imino-2-methylpentan-2-amino-Rh(III) Complexes through Metal-Assisted Intramolecular Aldol-Type Condensation of Two Acetimino Ligands
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- 作者：José ; Vicente ; Marí ; a-Teresa Chicote ; Rita Guerrero ; Inmaculada Vicente-Herná ; ndez ; and Miguel M. Alvarez-Falcó ; n
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：January 9, 2006
- 年：2006
- 卷：45
- 期：1
- 页码：181 - 188
- 全文大小：203K
- 年卷期：v.45,no.1(January 9, 2006)
- ISSN：1520-510X
文摘
[Rh(Cp*)Cl(
-Cl)]2 (Cp* = pentamethylcyclopentadienyl) reacts (i) with [Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give[Rh(Cp*)(-Cl)(NH=CMe2)]2(ClO4)2 (1), which in turn reacts with PPh3 (1:2) to give [Rh(Cp*)Cl(NH=CMe2)(PPh3)]ClO4 (2), and (ii) with [Ag(NH=CMe2)2]ClO4 (1:2 or 1:4) to give [Rh(Cp*)Cl(NH=CMe2)2]ClO4 (3) or [Rh(Cp*)(NH=CMe2)3](ClO4)2·H2O (4·H2O), respectively. Complex 3 reacts (i) with XyNC (1:1, Xy = 2,6-dimethylphenyl) togive [Rh(Cp*)Cl(NH=CMe2)(CNXy)]ClO4 (5), (ii) with Tl(acac) (1:1, acacH = acetylacetone) or with [Au(acac)(PPh3)] (1:1) to give [Rh(Cp*)(acac)(NH=CMe2)]ClO4 (6), (iii) with [Ag(NH=CMe2)2]ClO4 (1:1) to give 4, and (iv)with (PPN)Cl (1:1, PPN = Ph3P=N=PPh3) to give [Rh(Cp*)Cl(imam)]Cl (7·Cl), which contains the imam ligand(N,N-NH=C(Me)CH2C(Me)2NH2 = 4-imino-2-methylpentan-2-amino) that results from the intramolecular aldol-typecondensation of the two acetimino ligands. The homologous perchlorate salt (7·ClO4) can be prepared from 7·Cland AgClO4 (1:1), by treating 3 with a catalytic amount of Ph2C=NH, in an atmosphere of CO, or by reacting 4with (PPN)Cl (1:1). The reactions of 7·ClO4 with AgClO4 and PTo3 (1:1:1, To = C6H4Me-4) or XyNC (1:1:1) give[Rh(Cp*)(imam)(PTo3)](ClO4)2·H2O (8) or [Rh(Cp*)(imam)(CNXy)](ClO4)2 (9), respectively. The crystal structures of3 and 7·Cl have been determined.
-Cl)]2 (Cp* = pentamethylcyclopentadienyl) reacts (i) with [Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give[Rh(Cp*)(-Cl)(NH=CMe2)]2(ClO4)2 (1), which in turn reacts with PPh3 (1:2) to give [Rh(Cp*)Cl(NH=CMe2)(PPh3)]ClO4 (2), and (ii) with [Ag(NH=CMe2)2]ClO4 (1:2 or 1:4) to give [Rh(Cp*)Cl(NH=CMe2)2]ClO4 (3) or [Rh(Cp*)(NH=CMe2)3](ClO4)2·H2O (4·H2O), respectively. Complex 3 reacts (i) with XyNC (1:1, Xy = 2,6-dimethylphenyl) togive [Rh(Cp*)Cl(NH=CMe2)(CNXy)]ClO4 (5), (ii) with Tl(acac) (1:1, acacH = acetylacetone) or with [Au(acac)(PPh3)] (1:1) to give [Rh(Cp*)(acac)(NH=CMe2)]ClO4 (6), (iii) with [Ag(NH=CMe2)2]ClO4 (1:1) to give 4, and (iv)with (PPN)Cl (1:1, PPN = Ph3P=N=PPh3) to give [Rh(Cp*)Cl(imam)]Cl (7·Cl), which contains the imam ligand(N,N-NH=C(Me)CH2C(Me)2NH2 = 4-imino-2-methylpentan-2-amino) that results from the intramolecular aldol-typecondensation of the two acetimino ligands. The homologous perchlorate salt (7·ClO4) can be prepared from 7·Cland AgClO4 (1:1), by treating 3 with a catalytic amount of Ph2C=NH, in an atmosphere of CO, or by reacting 4with (PPN)Cl (1:1). The reactions of 7·ClO4 with AgClO4 and PTo3 (1:1:1, To = C6H4Me-4) or XyNC (1:1:1) give[Rh(Cp*)(imam)(PTo3)](ClO4)2·H2O (8) or [Rh(Cp*)(imam)(CNXy)](ClO4)2 (9), respectively. The crystal structures of3 and 7·Cl have been determined.