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Preparation, Structural Characterization, and Reactions of Tantalum-Alkyne Complexes TaCl3(R1C⋮CR2)L2 (L2 = DME, Bipy, and TMEDA; L = Py)

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    Preparation, Structural Characterization, and Reactions of Tantalum-Alkyne Complexes TaCl3(R1C⋮CR2)L2 (L2 = DME, Bipy, and TMEDA; L = Py)
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    Department of Applied Chemistry, Faculty of Engineering, Okayama University, Tsushima, Okayama 700-8530, Japan, and Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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    Organometallics

    Cite this: Organometallics 2003, 22, 3, 464–472
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    https://doi.org/10.1021/om020510x
    Published January 8, 2003
    Copyright © 2003 American Chemical Society
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    Abstract

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    Tantalum-alkyne complexes with the general formula TaCl3(R1C⋮CR2)(dme) (1a, R1 = R2 = Et; 1b, R1 = R2 = n-C5H11; 1c, R1 = Ph, R2 = Me; 1d, R1 = R2 = Ph; DME = 1,2-dimethoxyethane) were synthesized by treatment of the corresponding alkynes with a low-valent tantalum derived by reduction of tantalum pentachloride with zinc powder in a mixed solvent of toluene and DME. The DME ligand can be replaced by 2 equiv of pyridine to afford the corresponding dipyridine complexes TaCl3(R1C⋮CR2)(py)2 (2a, R1 = R2 = Et; 2b, R1 = R2 = n-C5H11; 2c, R1 = Ph, R2 = Me; 2d, R1 = R2 = Ph). Additionally, the reaction of 1a with the bidentate nitrogen ligands bipyridine and N,N,N‘,N‘-tetramethyethylenediamine (= TMEDA) gave TaCl3(EtC⋮CEt)(bipy) (3) and TaCl3(EtC⋮CEt)(tmeda) (4), respectively. The η2- and 4e-coordination mode of an alkyne with a large contribution of a metalacyclopropene canonical structure was revealed by spectroscopic methods (NMR and IR) and crystallographic analyses of 1a, 1c, 2a, and 4. The reactivies of the tantalum-3-hexyne complexes 1a, 2a, 3, and 4 toward 3-phenylpropanal were investigated. Only the pyridine complex 2a reacted with a stoichiometric amount of the aldehyde to afford the corresponding allylic alcohol in 77% yield upon hydrolysis. The reaction proceeded via an oxatantalacyclopentene species.

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     Okayama University.

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     Osaka University.

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    Structural drawings of 1a, 1c, 2a, and 4 and tables of X-ray crystallographic data, atomic coordinates, anisotropic thermal parameters, and a complete list of bond distances and angles are included. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Organometallics

    Cite this: Organometallics 2003, 22, 3, 464–472
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om020510x
    Published January 8, 2003
    Copyright © 2003 American Chemical Society
    Request reuse permissions

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