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Fe–Li Interactions in Ferrocenyllithium Compounds
Author(s) -
Malastová Andrea,
Vallo Ján,
Almássy Ambroz,
Pitoňák Michal,
Neogrády Pavel,
Šebesta Radovan
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201601114
Subject(s) - chemistry , intramolecular force , methyllithium , natural bond orbital , computational chemistry , lone pair , atomic orbital , ferrocene , density functional theory , ring (chemistry) , crystallography , electron , stereochemistry , molecule , organic chemistry , physics , electrode , quantum mechanics , electrochemistry
Intermetallic Fe–Li interactions likely occur during some stereoselective lithiation reactions of ferrocene derivatives. The nature of this interaction was assessed for a ferrocene–methyllithium complex as a model system by coupled‐cluster methods [CCSD(T)]. The CCSD(T) calculations predicted an interaction energy of –38.0 kJ mol –1 and an Fe–Li distance of 2.75 Å. The abilities of commonly used DFT functionals to describe this interaction were also screened. The best agreement of the structural parameters (energy and Fe–Li distance) with the CCSD(T) results was achieved with the dispersion‐corrected TPSS functional. DFT calculations were also used for natural bond orbital analysis of the intramolecular Fe–Li interactions in benzylferrocene ortho ‐lithiated at the phenyl ring. This dimetallic bond can be explained as a donor–acceptor orbital interaction between the Fe lone pair or the C–Fe bonding electrons with the empty Li orbitals.