A homologous series of regioselectively tetradeprotonated group 8 metallocenes: New inverse crown ring compounds synthesized via a mixed sodium-magnesium tris(diisopropylamide) synergic base

Prokopis C. Andrikopoulos, David R. Armstrong, William Clegg, Carly J. Gilfillan, Eva Hevia, Alan R. Kennedy, Robert E. Mulvey, Charles T. O'Hara, John A. Parkinson, Duncan M. Tooke

Research output: Contribution to journalArticle

97 Citations (Scopus)

Abstract

Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [{M(C5H3)(2)}Na4Mg4(i-Pr2N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular 'inverse crown' structure comprising a 16-membered [(NaNMgN)(4)](4+) 'host' ring and a metallocenetetraide [M(C5H3)(2)](4-) 'guest' core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements.
Original languageEnglish
Pages (from-to)11612-11620
Number of pages8
JournalJournal of the American Chemical Society
Volume126
Issue number37
Early online date26 Aug 2004
DOIs
Publication statusPublished - 22 Sep 2004

Keywords

  • alkali metal-magnesium
  • molecular-orbital methods
  • gaussian-type basis
  • organic-molecules
  • crystal-structure
  • ferrocene
  • chemistry
  • complexes
  • block
  • mercuracarborands

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