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    Early transition metal complexes with pi donor ligands and their reaction with alkynes.

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    Author
    Chao, Yuan-Wei.
    Issue Date
    1993
    Keywords
    Dissertations, Academic.
    Chemistry, Inorganic.
    Committee Chair
    Wigley, David E.
    
    Metadata
    Show full item record
    Publisher
    The University of Arizona.
    Rights
    Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
    Abstract
    A one step procedure for the preparation of new group 5 amido halides M(NEt₂)ₓCl₅₋ₓ (x = 1, 2, 3), imido halides M(=NAr)Cl₃(L)₂, and group 4 and 5 phenoxide halides. These complexes are obtained easily from the metal halides and trimethylsilyl reagents such as Me₃SiNR₂, Me₃SiNHAr, and Me₃SiOAr. The dimeric amides [M(NEt₂)₂Cl₃]₂ (M = Nb, Ta), the dimeric imide [Ta(=NAr)Cl₃(NH₂Ar)]₂, and the polymeric imide [Ta(=NAr)Cl₃(NH₂Ar)](n) are also prepared in a single step. The use of Me₃SiNR₂ and Me₃SiOAr compounds as amidation and alkoxylation reagents can be extended to prepare the alkoxide amides Ta(NEt₂)(OAr)Cl₃(OEt₂), Ta(NEt₂)(OAr)₂Cl₂(OEt₂), and Ta(OAr)(OAr')Cl₃(OEt₂). When these complexes are reduced using 2 equiv of NaHg in the presence of the appropriate alkyne, the d² alkyne adducts or cycloadducts of the form (alkyne)Ta(NEt₂)(m)X(3-m) (m = 1, 2), (alkyne)Ta(=NAr)X(py)₂, and (R₃CC=CHCH=CCR₃))Ta(=NAr)X(py)₂ (X = OAr, Cl), and (η⁶-C₆Et₆)Ta(OAr)Cl₂, (η⁶-C₆Me₆)Ta(OAr')Cl, (R₃CC=CHCH=CCR₃)Ta(OAr)Cl₂, and (alkyne)Nb(DIPP)₃ are formed. CpTa(NEt₂)₂Cl₂ (Cp = C₅H₅⁻) forms from the reaction of Ta(NEt₂)₂Cl₃(OEt₂) and NaCp. A low yield of [CpTa(NEt₂)₂H₂]₂ is isolated from CpTa(NEt₂)₂Cl₂ and 2 equiv of LiNHAr. The reaction of Ta(NEt₂)₂Cl₃(OEt₂) with various equiv of LiNHAr provides the mono(imido) complex Ta(=NAr)(NEt₂)Cl₂(L)₂, bis(imido) complex Ta(=NAr)₂Cl(py)₂, and tris(imido)complexes [Ta(=NAr)₃(NHAr)]⁻. The analogous complexes of niobium, [Nb(=NAr)(NEt₂)Cl₂(NHEt₂)]₂, Nb(=NAr)₂Cl(py)₂, and [Nb(=NAr)₃(NHAr)]⁻ are prepared from [Nb(NEt₂)₂Cl₃]₂ by a parallel procedure. Preliminary results, not always reproducible, for the syntheses of Li[Ta(=NAr)₃(py)] are also reported. The reaction of MCl₄ (M = Zr, Hf) with 4 equiv of LiNHAr in the presence of donor solvents provides the imido complexes M(=NAr)(NHAr)₂(L)₂.
    Type
    text
    Dissertation-Reproduction (electronic)
    Degree Name
    Ph.D.
    Degree Level
    doctoral
    Degree Program
    Chemistry
    Graduate College
    Degree Grantor
    University of Arizona
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