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Isomeric commo ‐Ferracarboranes: meso ‐, dd/ll ‐[PPh 3 R][ commo ‐Fe(2,4‐ closo ‐C 2 B 8 H 10 ) 2 ] and Their Bimetal Ferra–Copper Zwitterion Derivatives
Author(s) -
Balagurova Elena V.,
Silivonenko Anastasia I.,
Kostyukovich Alexander Yu.,
D'yachihin Dmitrii I.,
Smol'yakov Alexander F.,
Dolgushin Fedor M.,
Minin Vadim V.,
Peregudova Svetlana M.,
Chizhevsky Igor T.
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.201700571
Subject(s) - chemistry , crystallography , electron paramagnetic resonance , paramagnetism , carborane , x ray crystallography , crystal structure , copper , single crystal , anhydrous , stereochemistry , diffraction , nuclear magnetic resonance , physics , organic chemistry , quantum mechanics , optics
The reaction of [Na][C 2 B 8 H 11 ] with anhydrous FeCl 2 in THF affords a mixture of dd / ll and meso isomers of anionic paramagnetic commo ‐ferracarborane [Ph 3 PR][ commo ‐1,1′‐Fe( closo ‐2,4‐C 2 B 8 H 10 ) 2 ] ( meso , R = Me: 1a ; meso , Et: 1b ; dd/ll , R = Me: 2a ; dd/ll , R = Et: 2b ) with unusual closo geometry. Both dd / ll and meso isomers were successfully isolated and their structures were determined using single‐crystal X‐ray diffraction studies. Their paramagnetic properties were confirmed with EPR spectra and their oxidative–reductive properties were investigated using cyclic voltammetry. It was shown that facile dd / ll → meso and meso → dd / ll transformations, leading to equilibrium in CH 2 Cl 2 solution, occur. Quantum‐chemical calculations of the isomer‐to‐isomer transformations were performed. Ferra–copper zwitterionic complexes [3,3′,6,7′‐ exo ‐{Ph 3 PCu}‐3,3′,6,7′‐(µ‐H) 4 ‐ commo ‐1,1′‐Fe(2,4‐C 2 B 8 H 8 ) 2 ] and [3,3′,6,6′‐ exo ‐{Ph 3 PCu}‐3,3′,6,6′‐(µ‐H) 4 ‐ commo ‐1,1′‐Fe(2,4‐C 2 B 8 H 8 ) 2 ] were synthesized and their structures were determined by single‐crystal X‐ray diffraction studies.