On the Reactivity Toward Ketones of New Methyl Amino Complexes of Rh(III) and Ag(I). Synthesis of Ortho-Rhodiated Acetophenone Methyl Imine Complexes

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• 作者：José ; Vicente ; Marí ; a Teresa Chicote ; Inmaculada Vicente-Hern&aacute ; ndez ; Delia Bautista
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：October 15, 2007
• 年：2007
• 卷：46
• 期：21
• 页码：8939 - 8949
• 全文大小：241K
• 年卷期：v.46,no.21(October 15, 2007)
• ISSN：1520-510X

文摘

MeNH₂ reacts with silver salts AgX (2:1) to give [Ag(NH₂Me)₂]X [X = TfO = CF₃SO₃ (1·TfO) and ClO₄ (1·ClO₄)].Neutral mono(amino) Rh(III) complexes [Rh(Cp*)Cl₂(NH₂R)] [R = Me (2a), To = C₆H₄Me-4 (2b)] have been preparedby reacting [Rh(Cp*)Cl(-Cl)]₂ with RNH₂ (1:2). The following cationic methyl amino complexes have also beenprepared: [Rh(Cp*)Cl(NH₂Me)(PPh₃)]TfO (3·TfO), from [Rh(Cp*)Cl₂(PPh₃)] and 1·TfO (1:1); [Rh(Cp*)Cl(NH₂R)₂]X,where R = Me, X = Cl, (4a·Cl), from [Rh(Cp*)Cl(-Cl)]₂ and MeNH₂ (1:4), or R = Me, X = ClO₄ (4a·ClO₄), from4a·Cl and NaClO₄ (1:4.8), or R = To, X = TfO (4b·TfO), from [Rh(Cp*)Cl(-Cl)]₂, ToNH₂ and TlTfO (1:4:2);[Rh(Cp*)(NH₂Me)(^tBubpy)](TfO)₂ (^tBubpy = 4,4'-di-tert-butyl-2,2'-bipyridine, 5·TfO), from 2a, TlTfO and ^tBubpy (1:2:1); [Rh(Cp*)(NH₂Me)₃](TfO)₂ (6·TfO) from [Rh(Cp*)Cl(-Cl)]₂ and 1·TfO (1:4). 2-6 constitute the first family ofmethyl amino complexes of rhodium. 1 and 4a·ClO₄ react with acetone to give, respectively, the methyl iminocomplexes [Ag{N(Me)=CMe₂}₂]X [X = TfO (7·TfO), ClO₄ (7·ClO₄)], and [Rh(Cp*)Cl(Me-imam)]ClO₄ [8·ClO₄, Me-imam = N,N'-N(Me)=C(Me)CH₂C(Me)₂NHMe]. 7·X (X = TfO, ClO₄) are new members of the small family ofmethyl acetimino complexes of any metal whereas 8·ClO₄ results after a double acetone condensation to give thecorresponding bis(methyl acetimino) complex and an aldol-like condensation of the two imino ligands. The acetiminocomplex [Ag(NH=CMe₂)₂]ClO₄ reacts with [Rh(Cp*)Cl(imam)]ClO₄ [1:1, imam = N,N'-NH=C(Me)CH₂C(Me)₂NH₂]to give [Rh(Cp*)(imam)(NH=CMe₂)](ClO₄)₂ (9a·ClO₄). 8·ClO₄ reacts with AgClO₄ (1:1) in MeCN to give [Rh(Cp*)(Me-imam)(NCMe)](ClO₄)₂ (9b·ClO₄), which in turn reacts with XyNC (Xy = C₆H₃Me₂-2,6) or with MeNH₂ (1:1) togive [Rh(Cp*)(Me-imam)L](ClO₄)₂ [L = XyNC (9c·ClO₄), MeNH₂ (9d·ClO₄)]. 6·TfO reacts with acetophenone togive [Rh(Cp*){C,N-C₆H₄C(Me)=N(Me)-2}(NH₂Me)]TfO (10a·TfO), the first complex resulting from such a condensationand cyclometalation reaction. In turn, 10a·TfO reacts with isocyanides RNC (1:1) at room temperature to give[Rh(Cp*){C,N-C₆H₄C(Me)=NMe-2}(CNR)]TfO [R = ^tBu (10b·TfO), Xy (10c·TfO)], or 1:12 at 60 C to give [Rh(Cp*){C,N-C(=NXy)C₆H₄C(Me)=N(Me)-2}(CNXy)]TfO (11·TfO). The crystal structures of 9a·ClO₄·acetone-d₆, 9c·ClO₄, and 10a·TfO have been determined.