关于铑（III）和银（I）的新型甲基氨基配合物对酮的反应活性。邻位铑化苯乙酮甲基亚胺配合物的合成。
On the reactivity toward ketones of new methyl amino complexes of Rh(III) and Ag(I). Synthesis of ortho-rhodiated acetophenone methyl imine complexes.
作者信息
Vicente José, Chicote María Teresa, Vicente-Hernandez Inmaculada, Bautista Delia
机构信息
Grupo de Química OrganometAlica, Departamento de Química Inorgánica, Universidad de Murcia, Aptdo. 4021, 30071 Murcia, Spain.
出版信息
Inorg Chem. 2007 Oct 15;46(21):8939-49. doi: 10.1021/ic700963h. Epub 2007 Sep 20.
MeNH(2) reacts with silver salts AgX (2:1) to give [Ag(NH(2)Me)(2)]X [X = TfO = CF(3)SO(3) (1.TfO) and ClO(4) (1.ClO(4))]. Neutral mono(amino) Rh(III) complexes [Rh(Cp*)Cl(2)(NH(2)R)] [R = Me (2a), To = C(6)H(4)Me-4 (2b)] have been prepared by reacting Rh(Cp*)Cl(mu-Cl) with RNH(2) (1:2). The following cationic methyl amino complexes have also been prepared: [Rh(Cp*)Cl(NH(2)Me)(PPh(3))]TfO (3.TfO), from [Rh(Cp*)Cl(2)(PPh(3))] and 1.TfO (1:1); [Rh(Cp*)Cl(NH(2)R)2]X, where R = Me, X = Cl, (4a.Cl), from [Rh(Cp*)Cl(mu-Cl)]2 and MeNH2 (1:4), or R = Me, X = ClO4 (4a.ClO4), from 4a.Cl and NaClO4 (1:4.8), or R = To, X = TfO (4b.TfO), from Rh(Cp*)Cl(mu-Cl), ToNH(2) and TlTfO (1:4:2); Rh(Cp*)(NH(2)Me)(tBubpy)(2) (tBubpy = 4,4'-di-tert-butyl-2,2'-bipyridine, 5.TfO), from 2a, TlTfO and tBubpy (1:2:1); Rh(Cp*)(NH(2)Me)(3)2 (6.TfO) from Rh(Cp*)Cl(mu-Cl) and 1.TfO (1:4). 2-6 constitute the first family of methyl amino complexes of rhodium. 1 and 4a.ClO(4) react with acetone to give, respectively, the methyl imino complexes [Ag{N(Me)=CMe(2)}()]X [X = TfO (7.TfO), ClO(4) (7.ClO(4))], and [Rh(Cp*)Cl(Me-imam)]ClO(4) [8.ClO(4), Me-imam = N,N'-N(Me)=C(Me)CH(2)C(Me)(2)NHMe]. 7.X (X = TfO, ClO(4)) are new members of the small family of methyl acetimino complexes of any metal whereas 8.ClO4 results after a double acetone condensation to give the corresponding bis(methyl acetimino) complex and an aldol-like condensation of the two imino ligands. The acetimino complex [Ag(NH=CMe(2))(2)]ClO(4) reacts with [Rh(Cp*)Cl(imam)]ClO(4) [1:1, imam = N,N'-NH=C(Me)CH(2)C(Me)(2)NH(2)] to give Rh(Cp*)(imam)(NH=CMe(2))(2) (9a.ClO(4)). 8.ClO(4) reacts with AgClO(4) (1:1) in MeCN to give Rh(Cp*)(Me-imam)(NCMe)2 (9b.ClO(4)), which in turn reacts with XyNC (Xy = C(6)H(3)Me(2)-2,6) or with MeNH(2) (1:1) to give Rh(Cp*)(Me-imam)L(2) [L = XyNC (9c.ClO(4)), MeNH(2) (9d.ClO(4))]. 6.TfO reacts with acetophenone to give [Rh(Cp*){C,N-C(6)H(4)C(Me)=N(Me)-2}(NH(2)Me)]TfO (10a.TfO), the first complex resulting from such a condensation and cyclometalation reaction. In turn, 10a.TfO reacts with isocyanides RNC (1:1) at room temperature to give [Rh(Cp*){C,N-C(6)H(4)C(Me)=NMe-2}(CNR)]TfO [R = tBu (10b.TfO), Xy (10c.TfO)], or 1:12 at 60 degrees C to give [Rh(Cp*){C,N-C(=NXy)C(6)H(4)C(Me)=N(Me)-2}(CNXy)]TfO (11.TfO). The crystal structures of 9a.ClO(4).acetone-d6, 9c.ClO(4), and 10a.TfO have been determined.
甲胺（MeNH₂）与银盐AgX（2:1）反应生成[Ag(NH₂Me)₂]X [X = TfO = CF₃SO₃（1.TfO）和ClO₄（1.ClO₄）]。通过使[Rh(Cp*)Cl(μ-Cl)]₂与RNH₂（1:2）反应制备了中性单（氨基）铑（III）配合物[Rh(Cp*)Cl₂(NH₂R)] [R = Me（2a），To = C₆H₄Me - 4（2b）]。还制备了以下阳离子甲基氨基配合物：[Rh(Cp*)Cl(NH₂Me)(PPh₃)]TfO（3.TfO），由[Rh(Cp*)Cl₂(PPh₃)]和1.TfO（1:1）反应得到；[Rh(Cp*)Cl(NH₂R)₂]X，其中R = Me，X = Cl，（4a.Cl），由[Rh(Cp*)Cl(μ-Cl)]₂和甲胺（1:4）反应得到，或者R = Me，X = ClO₄（4a.ClO₄），由4a.Cl和高氯酸钠（1:4.8）反应得到，或者R = To，X = TfO（4b.TfO），由[Rh(Cp*)Cl(μ-Cl)]₂、对甲苯胺和三氟甲磺酸铊（1:4:2）反应得到；Rh(Cp*)(NH₂Me)(tBubpy)₂（tBubpy = 4,4'-二叔丁基-2,2'-联吡啶，5.TfO），由2a、三氟甲磺酸铊和tBubpy（1:2:1）反应得到；Rh(Cp*)(NH₂Me)₃₂（6.TfO）由[Rh(Cp*)Cl(μ-Cl)]₂和1.TfO（1:4）反应得到。2 - 6构成了铑的第一类甲基氨基配合物。1和4a.ClO₄与丙酮反应分别生成甲基亚氨基配合物[Ag{N(Me)=CMe₂}]X [X = TfO（7.TfO），ClO₄（7.ClO₄）]，以及[Rh(Cp*)Cl(Me - imam)]ClO₄ [8.ClO₄，Me - imam = N,N'-N(Me)=C(Me)CH₂C(Me)₂NHMe]。7.X（X = TfO，ClO₄）是任何金属的甲基乙亚氨基配合物小家族的新成员，而8.ClO₄是经过双丙酮缩合得到相应的双（甲基乙亚氨基）配合物以及两个亚氨基配体的类似羟醛缩合反应后得到的。乙亚氨基配合物[Ag(NH = CMe₂)₂]ClO₄与[Rh(Cp*)Cl(imam)]ClO₄ [1:1，imam = N,N'-NH = C(Me)CH₂C(Me)₂NH₂]反应生成Rh(Cp*)(imam)(NH = CMe₂)₂（9a.ClO₄）。8.ClO₄在乙腈中与高氯酸银（1:1）反应生成Rh(Cp*)(Me - imam)(NCMe)₂（9b.ClO₄），后者依次与XyNC（Xy = C₆H₃Me₂ - 2,6）或与甲胺（1:1）反应生成Rh(Cp*)(Me - imam)L₂ [L = XyNC（9c.ClO₄），MeNH₂（9d.ClO₄）]。6.TfO与苯乙酮反应生成[Rh(Cp*){C,N - C₆H₄C(Me)=N(Me)-2}(NH₂Me)]TfO（10a.TfO），这是由这种缩合和环金属化反应得到的第一个配合物。反过来，10a.TfO在室温下与异腈RNC（1:1）反应生成[Rh(Cp*){C,N - C₆H₄C(Me)=NMe - 2}(CNR)]TfO [R = tBu（10b.TfO），Xy（10c.TfO）]，或者在60℃下与1:12的异腈反应生成[Rh(Cp*){C,N - C(=NXy)C₆H₄C(Me)=N(Me)-2}(CNXy)]TfO（11.TfO）。已测定了9a.ClO₄·丙酮 - d₆、9c.ClO₄和10a.TfO的晶体结构。
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