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Molecular mechanics of bridged ferrocene derivatives: Conformational energy surfaces of [3]‐, [4]‐ and [4 5 ] ferrocenophanes
Author(s) -
Rudziński Jerzy M.,
Ōsawa Eiji
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610050703
Subject(s) - chemistry , cyclopentadienyl complex , ferrocene , enantiomer , computational chemistry , potential energy , maxima and minima , crystallography , interpretation (philosophy) , stereochemistry , atomic physics , organic chemistry , catalysis , physics , mathematical analysis , mathematics , electrode , computer science , electrochemistry , programming language
A molecular mechanical model is presented which allows computational interpretation of stereodynamics in ferrocenophanes by using a simple form of bending potential for angles involving the central iron atom and extended to carbon atoms of different cyclopentadienyl rings. Potential energy surfaces of [3] ‐, [4] ‐ and [4 5 ] ferrocenophanes were studied in detail. For [3] ferrocenophane, the calculated energy barrier of the bridge reversal process agrees well with the experimental value. The previous interpretation of a rigid bridge in [4] ferrocenophane is questioned on the basis of the calculated low barriers. The predominance of experimentally indistinguishable enantiomeric pairs may be responsible for the misinterpretation. [4 5 ] Ferrocenophane is estimated to interconvert into D 5 ‐symmetric global energy minima over barriers of 13–15 kcal mol −1 through one‐by‐one flipping of five tetramethylene bridges.