Abstract
The reactions of the chlorosilyl‐substituted cyclopentadienyl niobium compound [Nb(η5‐C5H4SiMe2Cl)Cl4] (1) with 1 equiv. of 2‐methoxyethylamine, 3‐methoxypropylamine, and allylamine in toluene specifically afford the corresponding amine adducts [Nb(η5‐C5H4SiMe2Cl){NH2(CH2)nOMe}Cl4] (n = 2, 2; 3, 3) and [Nb(η5‐C5H4SiMe2Cl)(NH2CH2CH=CH2)Cl4] (4). In contrast, a similar reaction with 1,2‐phenylenediamine proceeds with the aminolysis of a Nb–Cl bond and the formation of the amido–amine compound [Nb(η5‐C5H4SiMe2Cl)(NHC6H4‐2‐κNH2)Cl3] (5). When such reactions are performed in the presence of 2 equiv. of an additional base, they progress through the double deprotonation of the primary amine group and the formation of a single product, the structure of which depends on the coordinating ability of the pendant donor end group. Thus, two different types of derivatives are obtained, constrained‐geometry complexes such as [Nb{η5‐C5H4SiMe2‐κN(CH2)2‐κOMe}Cl3] (6) and [Nb(η5‐C5H4SiMe2‐κNC6H4‐2‐κNH2)Cl3] (7) or imido derivatives such as [Nb(η5‐C5H4SiMe2Cl){N(CH2)3OMe}Cl2] (8) and [Nb(η5‐C5H4SiMe2Cl)(NCH2CHCH2)Cl2] (9). All of the compounds have been characterized by NMR spectroscopy, and the molecular structures of 2 and 6 have been determined by X‐ray diffraction methods.
Published Version
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