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A halogenophilic pathway in the reactions of transition metal carbonyl anions with [(η-iodobenzene)Cr(CO)]

Dalton Transactions, ISSN: 1477-9234, Vol: 43, Issue: 35, Page: 13392-13398
2014
  • 9
    Citations
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  • 17
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Metric Options:   Counts1 Year3 Year

Metrics Details

  • Citations
    9
    • Citation Indexes
      9
  • Captures
    17

Article Description

The paper provides the first example of formal nucleophilic substitution by the halogenophilic pathway in Cr(CO) complexes of haloarenes with metal carbonyl anions. All metal carbonyl anions examined attack [(η-iodobenzene)Cr(CO)] at halogen, which is shown by aryl carbanion scavenging with t-BuOH. The reaction with K[CpFe(CO) ] gives only the dehalogenated arene, but the reaction with K[Cp*Fe(CO)] (Cp* = η-C Me) results in nucleophilic substitution to give [(η-CHFeCp*(CO) )Cr(CO)]. Reaction with Na[Re(CO)] quantitatively gives the iodo(acyl)rhenate anion Na[(η-C HC(O)ReI(CO))Cr(CO)] and in the case of K[Mn(CO)] a mixture of σ-aryl complexes [(η-CHMn(CO))Cr(CO) ] and K[(η-CHMn(CO) I)Cr(CO)]. An analogous rhenium complex Na[(η-CHRe(CO)I)Cr(CO) ] is formed from the initial iodo(acyl)rhenate upon prolonged standing at 20 °C, and its structure (in the form of [NEt] salt) is established by X-ray diffraction analysis. The reaction of [(η-chlorobenzene)Cr(CO)] with K[CpFe(CO) ], in contrast, proceeds by the common S2Ar mechanism. © 2014 The Royal Society of Chemistry.

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