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Structure of Tricarbonyl(diene)iron Complexes in Solution. Variable‐Temperature Circular Dichroism of trans ‐μ‐(2,3,5,6‐Tetramethylidenebicyclo[2.2.2]octane)bis(tricarbonyliron) Complexes
Author(s) -
Gabioud Raphy,
Vogel Pierre
Publication year - 1986
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19860690413
Subject(s) - chemistry , octane , diene , stereochemistry , circular dichroism , crystallography , solvent , bicyclic molecule , organic chemistry , natural rubber
Abstract Optically pure (−)‐ trans ‐μ‐[(1 R ,2 R ,3 S ,4 S ,5 S ,6 R )‐ C ,2,3, C ‐η: C ,5,6, C ‐η‐(2,3,5,6,7‐pentamethylidenebicyclo[2.2.2]octane)]bis(tricarbonyliron) ((−)‐ 9 ), (−)‐ trans ‐μ‐[(1 R ,2 R ,3 S ,4 S ,5 S ,6 R ,7 S )‐ C ,2,3, C ‐η: C ,5,6, C ‐η‐(7‐methyl‐2,3,5,6‐tetramethylidenebicyclo[2.2.2]octane)]bis(tricarbonyliron) ((−)‐ 10 ), and (−)‐ trans ‐μ‐[(1 R ,2 R ,3 S ,4 S ,5 S ,6 R ,7 R )‐ C ,2,3, C ‐η: C ,5,6, C ‐η‐(2,3,5,6‐tetramethylidene(7D)bicyclo[2.2.2]octane)]bis(tricarbonyliron) ((−)‐ 16 ) have been prepared. Their CD spectra were solvent‐ and concentration‐independent, but temperature‐dependent, in accord with the existence of equilibria between rapidly interconverting diastereoisomeric species which can be interpreted as arising from distortions of the tricarbonyl(diene)iron units from the C s symmetry.