2. Academic Validation
  3. Synthesis of rhenabenzenes from the reactions of rhenacyclobutadienes with ethoxyethyne

Synthesis of rhenabenzenes from the reactions of rhenacyclobutadienes with ethoxyethyne

  • Chemistry. 2014 Nov 3;20(45):14885-99. doi: 10.1002/chem.201403186.
Ran Lin 1,  Ka-Ho Lee,  Ka Chun Poon,  Herman H Y Sung,  Ian D Williams,  Zhenyang Lin,  Guochen Jia
Affiliations

Affiliation

  • 1 Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong), Fax: (+852) 2358-1594.
PMID: 25220667 DOI: 10.1002/chem.201403186
Abstract

Treatment of Na[Re(CO)5 ] with RCCCO2 Et (R=phenyl, naphthalen-1-yl, phenanthren-9-yl and pyren-1-yl) followed by reaction with acetyl chloride and ethanol afforded the rhenacyclobutadienes Re{-C(R)C(CO2 Et)C(OEt)}(CO)4 . Reactions of these rhenacyclobutadienes with HCCOEt produced rhenabenzenes Re{-C(R)C(CO2 Et)C(OEt)CHC(OEt)}(CO)4 . Except for R=Ph, new rhenacyclobutadienes with pendant alkenyl substituents Re{-C(R)C(C(OEt)CH(CO2 Et))C(OEt)}(CO)4 were also isolated from these reactions. The NMR spectroscopic and X-ray structural data, as well as the aromatic stabilization energy (ASE) values suggest that the rhenabenzenes are aromatic, with extensive delocalized π character.

Keywords

aromaticity; metallabenzene; metallacycles; rhenium; structure elucidation.

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