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Redox-Induced Indenyl Slippage in [IndCpMoL<INF>2</INF>]<SUP>2+/+/0</SUP> Complexes

Authors :
Gamelas, C. A.
Herdtweck, E.
Lopes, J. P.
Romao, C. C.
Source :
Organometallics; February 15, 1999, Vol. 18 Issue: 4 p506-515, 10p
Publication Year :
1999

Abstract

The dicationic complexes [IndCpMoL&lt;INF&gt;2&lt;/INF&gt;]&lt;SUP&gt;2+&lt;/SUP&gt; (Ind = indenyl; Cp = cyclopentadienyl; &lt;BO&gt;1&lt;/BO&gt;, L&lt;INF&gt;2&lt;/INF&gt; = dppe; &lt;BO&gt;2&lt;/BO&gt;, L = PMe&lt;INF&gt;3&lt;/INF&gt;; &lt;BO&gt;4&lt;/BO&gt;, L&lt;INF&gt;2&lt;/INF&gt; = Bipy; &lt;BO&gt;5&lt;/BO&gt;, L&lt;INF&gt;2&lt;/INF&gt; = &lt;SUP&gt;t&lt;/SUP&gt;Bu&lt;INF&gt;2&lt;/INF&gt;bipy; &lt;BO&gt;6&lt;/BO&gt;, L&lt;INF&gt;2&lt;/INF&gt; = H&lt;INF&gt;2&lt;/INF&gt;biim; &lt;BO&gt;7&lt;/BO&gt;, L = CO and CNMe; &lt;BO&gt;8&lt;/BO&gt;, L = CNMe; &lt;BO&gt;9&lt;/BO&gt;, L = CN&lt;SUP&gt;t&lt;/SUP&gt;Bu; &lt;BO&gt;10&lt;/BO&gt;, L = NCMe and NMF; &lt;BO&gt;11&lt;/BO&gt;, L = NMF) were synthesized from [IndCpMoL‘&lt;INF&gt;2&lt;/INF&gt;]&lt;SUP&gt;2+&lt;/SUP&gt; (L‘ = CO, NCMe), [IndCpMo(NCMe)Cl]BF&lt;INF&gt;4&lt;/INF&gt;, or IndCpMoCl&lt;INF&gt;2&lt;/INF&gt; by ligand substitution. The neutral complexes (η&lt;SUP&gt;3&lt;/SUP&gt;-Ind)CpMoL&lt;INF&gt;2&lt;/INF&gt; (&lt;BO&gt;13&lt;/BO&gt;, L&lt;INF&gt;2&lt;/INF&gt; = dppe; &lt;BO&gt;14&lt;/BO&gt;, L = PMe&lt;INF&gt;3&lt;/INF&gt;; &lt;BO&gt;15&lt;/BO&gt;, L&lt;INF&gt;2&lt;/INF&gt; = Bipy; &lt;BO&gt;16&lt;/BO&gt;, L = CO and CNMe; &lt;BO&gt;17&lt;/BO&gt;, L = CN&lt;SUP&gt;t&lt;/SUP&gt;Bu) were obtained upon reduction of the respective dications with Cp&lt;INF&gt;2&lt;/INF&gt;Co. (η&lt;SUP&gt;3&lt;/SUP&gt;-Ind)CpMo(dppe) &lt;BO&gt;(13)&lt;/BO&gt; was also prepared by deprotonation of the cyclopentadiene cation [IndMo(η&lt;SUP&gt;4&lt;/SUP&gt;-C&lt;INF&gt;5&lt;/INF&gt;H&lt;INF&gt;6&lt;/INF&gt;)(dppe)]BF&lt;INF&gt;4&lt;/INF&gt; &lt;BO&gt;(12) &lt;/BO&gt;with NEt&lt;INF&gt;3&lt;/INF&gt;. The cyclic voltammograms of the dications present one reversible 2e reduction step from Mo(IV) to Mo(II) except for &lt;BO&gt;1&lt;/BO&gt;, &lt;BO&gt;2&lt;/BO&gt;, and &lt;BO&gt;6&lt;/BO&gt;, in which cases two reversible 1e waves are observed. The ring-slipped complexes (η&lt;SUP&gt;3&lt;/SUP&gt;-Ind)CpMoL&lt;INF&gt;2&lt;/INF&gt; and the parent dications present similar CV&#39;s. The X-ray crystal structures of [IndCpModppe][BF&lt;INF&gt;4&lt;/INF&gt;]&lt;INF&gt;2&lt;/INF&gt; and (η&lt;SUP&gt;3&lt;/SUP&gt;-Ind)CpMo(dppe) confirm the indenyl ring planar η&lt;SUP&gt;5&lt;/SUP&gt; coordination and slip-folded η&lt;SUP&gt;3&lt;/SUP&gt;, respectively.

Details

Language :
English
ISSN :
02767333 and 15206041
Volume :
18
Issue :
4
Database :
Supplemental Index
Journal :
Organometallics
Publication Type :
Periodical
Accession number :
ejs1153699

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