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Reactions of Butterfly Complex Anions of the Type [(μ-RTe)(μ-CO)Fe<INF>2</INF>(CO)<INF>6</INF>]<SUP>-</SUP> with Electrophiles. A New Route to μ<INF>4</INF>-Se-Containing Double-Butterfly Clusters. Crystal Structures of (μ-p-MeC<INF>6</INF>H<INF>4</INF>Te)(μ-PhCH<INF>2</INF>SC&dbd;S)Fe<INF>2</INF>(CO)<INF>6</INF> and [(μ-RTe)Fe<INF>2</INF>(CO)<INF>6</INF>]<INF>2</INF>(μ<INF>4</INF>-Se) (R = Ph, p-BrC<INF>6</INF>H<INF>4</INF>)

Authors :
Song, L.-C.
Hu, Q.-M.
Fan, H.-T.
Tang, M.-Y.
Yang, Z.-Y.
Lu, G.-L.
Source :
Organometallics; June 2002, Vol. 21 Issue: 12 p2468-2472, 5p
Publication Year :
2002

Abstract

The nucleophilic reaction of anions [(μ-RTe)(μ-CO)Fe&lt;INF&gt;2&lt;/INF&gt;(CO)&lt;INF&gt;6&lt;/INF&gt;]&lt;SUP&gt;-&lt;/SUP&gt; (&lt;BO&gt;3&lt;/BO&gt;) with CS&lt;INF&gt;2&lt;/INF&gt; and subsequent treatment with organic halides R‘X gave a series of R‘S-containing single-butterfly complexes (μ-RTe)(μ-R‘SC&amp;dbd;S)Fe&lt;INF&gt;2&lt;/INF&gt;(CO)&lt;INF&gt;6&lt;/INF&gt; (&lt;BO&gt;4a&lt;/BO&gt;−&lt;BO&gt;d&lt;/BO&gt;, R = Ph, p-MeC&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;; R‘ = Me, PhCH&lt;INF&gt;2&lt;/INF&gt;), whereas &lt;BO&gt;3&lt;/BO&gt; reacted with R‘NCS followed by treatment with CF&lt;INF&gt;3&lt;/INF&gt;CO&lt;INF&gt;2&lt;/INF&gt;H or MeI to afford the R‘HN- and R‘MeN-containing single-butterfly complexes (μ-RTe)(μ-R‘HNC&amp;dbd;S)Fe&lt;INF&gt;2&lt;/INF&gt;(CO)&lt;INF&gt;6&lt;/INF&gt; and (μ-RTe)(μ-R‘MeNC&amp;dbd;S)Fe&lt;INF&gt;2&lt;/INF&gt;(CO)&lt;INF&gt;6&lt;/INF&gt; (&lt;BO&gt;5a&lt;/BO&gt;−&lt;BO&gt;d, &lt;/BO&gt;R = Ph, p-MeC&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;; R‘ = Ph, PhCH&lt;INF&gt;2&lt;/INF&gt;). Interestingly, a series of double-butterfly μ&lt;INF&gt;4&lt;/INF&gt;-Se-containing complexes [(μ-RTe)Fe&lt;INF&gt;2&lt;/INF&gt;(CO)&lt;INF&gt;6&lt;/INF&gt;]&lt;INF&gt;2&lt;/INF&gt; (μ&lt;INF&gt;4&lt;/INF&gt;-Se) (&lt;BO&gt;6a&lt;/BO&gt;−&lt;BO&gt;e&lt;/BO&gt;, R = Et, Ph, p-MeC&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;, o-MeC&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;, p-BrC&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;) could be produced via a simple and new synthetic route involving a doubly nucleophilic reaction of anions &lt;BO&gt;3&lt;/BO&gt; with an electrophile SeCl&lt;INF&gt;2&lt;/INF&gt;. New complexes &lt;BO&gt;4a&lt;/BO&gt;−&lt;BO&gt;d&lt;/BO&gt;, &lt;BO&gt;5a&lt;/BO&gt;−&lt;BO&gt;d&lt;/BO&gt;, and &lt;BO&gt;6a&lt;/BO&gt;−&lt;BO&gt;e&lt;/BO&gt; derived from anions &lt;BO&gt;3&lt;/BO&gt; have been fully characterized by elemental analysis and IR, &lt;SUP&gt;1&lt;/SUP&gt;H NMR, &lt;SUP&gt;125&lt;/SUP&gt;Te NMR, and &lt;SUP&gt;77&lt;/SUP&gt;Se NMR (for &lt;BO&gt;6a&lt;/BO&gt;−&lt;BO&gt;e&lt;/BO&gt;) spectroscopies. The &lt;SUP&gt;125&lt;/SUP&gt;Te NMR spectra of the new complexes displayed only one singlet, indicating that they consist of only one isomer, either a(R) or e(R). This has been confirmed by crystal X-ray diffraction analyses of &lt;BO&gt;4d&lt;/BO&gt; (R = p-MeC&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;; R‘ = PhCH&lt;INF&gt;2&lt;/INF&gt;), &lt;BO&gt;6b&lt;/BO&gt; (R = Ph), and &lt;BO&gt;6e &lt;/BO&gt;(R = p-BrC&lt;INF&gt;6&lt;/INF&gt;H&lt;INF&gt;4&lt;/INF&gt;), in which the R groups are attached to bridged Te atoms by an equatorial type of bond.

Details

Language :
English
ISSN :
02767333 and 15206041
Volume :
21
Issue :
12
Database :
Supplemental Index
Journal :
Organometallics
Publication Type :
Periodical
Accession number :
ejs2248317
Full Text :
https://doi.org/10.1021/om020132w
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