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Synthesis and Characterization of the First Niobocene Germyl Complexes and Reactivity of Triphenylsilyl-, Triphenylgermyl-, and Triphenylstannylniobocene Derivatives. X-ray Molecular Structures of d<SUP>0</SUP> Nb(η<SUP>5</SUP>-C<INF>5</INF>H<INF>4</INF>SiMe<INF>3</INF>)<INF>2</INF>(H)<INF>2</INF>(EPh<INF>3</INF>) (E = Ge, Sn)

Authors :
Antinolo, A.
Carrillo-Hermosilla, F.
Castel, A.
Fajardo, M.
Fernandez-Baeza, J.
Lanfranchi, M.
Otero, A.
Pellinghelli, M. A.
Rima, G.
Satge, J.
Villasenor, E.
Source :
Organometallics; April 13, 1998, Vol. 17 Issue: 8 p1523-1529, 7p
Publication Year :
1998

Abstract

Thermal treatment of Nb(η&lt;SUP&gt;5&lt;/SUP&gt;-C&lt;INF&gt;5&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;SiMe&lt;INF&gt;3&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;(H)&lt;INF&gt;3&lt;/INF&gt; (&lt;BO&gt;1&lt;/BO&gt;) with the appropriate organogermanium hydrides (HGeR&lt;INF&gt;3&lt;/INF&gt;) and HSnPh&lt;INF&gt;3&lt;/INF&gt; gives the corresponding niobocene germyl hydrides Nb(η&lt;SUP&gt;5&lt;/SUP&gt;-C&lt;INF&gt;5&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;SiMe&lt;INF&gt;3&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;(H)&lt;INF&gt;2&lt;/INF&gt;(GeR&lt;INF&gt;3&lt;/INF&gt;), GeR&lt;INF&gt;3&lt;/INF&gt;&amp;dbd;GePh&lt;INF&gt;3&lt;/INF&gt; (&lt;BO&gt;2&lt;/BO&gt;), GePh&lt;INF&gt;2&lt;/INF&gt;H (&lt;BO&gt;3&lt;/BO&gt;), GeEt&lt;INF&gt;3&lt;/INF&gt; (&lt;BO&gt;4&lt;/BO&gt;), Ge(C&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;13&lt;/INF&gt;)&lt;INF&gt;3&lt;/INF&gt; (&lt;BO&gt;5&lt;/BO&gt;), Ge&lt;SUP&gt;i&lt;/SUP&gt;Am&lt;INF&gt;3&lt;/INF&gt; (&lt;SUP&gt;i&lt;/SUP&gt;Am = CH&lt;INF&gt;2&lt;/INF&gt;CH&lt;INF&gt;2&lt;/INF&gt;CH(CH&lt;INF&gt;3&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;) (&lt;BO&gt;6&lt;/BO&gt;), Ge(C&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;13&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;Cl (&lt;BO&gt;7&lt;/BO&gt;), Ge&lt;SUP&gt;i&lt;/SUP&gt;Am&lt;INF&gt;2&lt;/INF&gt;Cl (&lt;BO&gt;8&lt;/BO&gt;), Ge(C&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;13&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;H (&lt;BO&gt;9&lt;/BO&gt;), Ge&lt;SUP&gt;i&lt;/SUP&gt;Am&lt;INF&gt;2&lt;/INF&gt;H (&lt;BO&gt;10&lt;/BO&gt;), and Nb(η&lt;SUP&gt;5&lt;/SUP&gt;-C&lt;INF&gt;5&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;SiMe&lt;INF&gt;3&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;(H)&lt;INF&gt;2&lt;/INF&gt;(SnPh&lt;INF&gt;3&lt;/INF&gt;) (&lt;BO&gt;11&lt;/BO&gt;) in good yields. Spectroscopic data indicate the presence of only one of the two possible structural isomers in which the germyl or stannyl group is in the equatorial plane with a symmetrical structure. Reactivity studies on the series Nb(η&lt;SUP&gt;5&lt;/SUP&gt;-C&lt;INF&gt;5&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;SiMe&lt;INF&gt;3&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;(H)&lt;INF&gt;2&lt;/INF&gt;(ER&lt;INF&gt;3&lt;/INF&gt;), E = Si (&lt;BO&gt;12&lt;/BO&gt;), Ge (&lt;BO&gt;2&lt;/BO&gt;), Sn (&lt;BO&gt;11&lt;/BO&gt;), were carried out. &lt;BO&gt;12&lt;/BO&gt; reacts with H&lt;INF&gt;2&lt;/INF&gt; to give &lt;BO&gt;1&lt;/BO&gt;, but &lt;BO&gt;2&lt;/BO&gt; and &lt;BO&gt;11&lt;/BO&gt; were unreactive toward this reagent. Furthermore, a similar behavior was observed with CO and CN(2,6-Me&lt;INF&gt;2&lt;/INF&gt;C&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;3&lt;/INF&gt;). Thus, &lt;BO&gt;12&lt;/BO&gt; reacts with these reagents to give rise, after elimination of HSiPh&lt;INF&gt;3&lt;/INF&gt;, to Nb(η&lt;SUP&gt;5&lt;/SUP&gt;-C&lt;INF&gt;5&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;SiMe&lt;INF&gt;3&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;(H)(CO) and Nb(η&lt;SUP&gt;5&lt;/SUP&gt;-C&lt;INF&gt;5&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;SiMe&lt;INF&gt;3&lt;/INF&gt;)&lt;INF&gt;2&lt;/INF&gt;(H)(CN(2,6-Me&lt;INF&gt;2&lt;/INF&gt;C&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;3&lt;/INF&gt;)), respectively, while &lt;BO&gt;2&lt;/BO&gt; and &lt;BO&gt;11&lt;/BO&gt; do not react. Reactions of &lt;BO&gt;12&lt;/BO&gt; with HGePh&lt;INF&gt;3&lt;/INF&gt; and HSnPh&lt;INF&gt;3&lt;/INF&gt; and of &lt;BO&gt;2&lt;/BO&gt; with HSnPh&lt;INF&gt;3&lt;/INF&gt; gave σ-bond metathesis products, but no reactions were observed between &lt;BO&gt;2&lt;/BO&gt; and HSiPh&lt;INF&gt;3&lt;/INF&gt; or between &lt;BO&gt;11&lt;/BO&gt; and HSiPh&lt;INF&gt;3&lt;/INF&gt; or &lt;BO&gt;11&lt;/BO&gt; and HGePh&lt;INF&gt;3&lt;/INF&gt;. The kinetics of these processes have been studied by &lt;SUP&gt;1&lt;/SUP&gt;H NMR spectroscopy and indicated the following reactivity trends Nb−SiPh&lt;INF&gt;3&lt;/INF&gt; &gt; Nb−GePh&lt;INF&gt;3&lt;/INF&gt; &gt; Nb−SnPh&lt;INF&gt;3&lt;/INF&gt; for the different processes considered. The X-ray molecular structures of &lt;BO&gt;2&lt;/BO&gt; and &lt;BO&gt;11&lt;/BO&gt; were established by diffraction studies. The two isostructural complexes show a bent-sandwich coordination with the two hydrides flanking either side of the Nb−Ge and Nb−Sn bonds (2.710(1), 2.830(1) &#197; in &lt;BO&gt;2&lt;/BO&gt; and &lt;BO&gt;11&lt;/BO&gt;, respectively).

Details

Language :
English
ISSN :
02767333 and 15206041
Volume :
17
Issue :
8
Database :
Supplemental Index
Journal :
Organometallics
Publication Type :
Periodical
Accession number :
ejs1152933

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