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Ligand Effects on the Electronic Structure of Heteroleptic Antimony‐Centered Radicals
Author(s) -
Helling Christoph,
Cutsail George E.,
Weinert Hanns,
Wölper Christoph,
Schulz Stephan
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202000586
Subject(s) - chemistry , delocalized electron , radical , unpaired electron , substituent , ligand (biochemistry) , crystallography , metal , antimony , stereochemistry , cyclic voltammetry , crystal structure , electronic structure , inorganic chemistry , electrochemistry , computational chemistry , organic chemistry , receptor , biochemistry , electrode
We report on the structures of three unprecedented heteroleptic Sb‐centered radicals [L(Cl)Ga](R)Sb . ( 2‐R , R=B[N(Dip)CH] 2 2‐B , 2,6‐Mes 2 C 6 H 3 2‐C , N(SiMe 3 )Dip 2‐N ) stabilized by one electropositive metal fragment [L(Cl)Ga] (L=HC[C(Me)N(Dip)] 2 , Dip=2,6‐ i ‐Pr 2 C 6 H 3 ) and one bulky B‐ ( 2‐B ), C‐ ( 2‐C ), or N‐based ( 2‐N ) substituent. Compounds 2‐R are predominantly metal‐centered radicals. Their electronic properties are largely influenced by the electronic nature of the ligands R, and significant delocalization of unpaired‐spin density onto the ligands was observed in 2‐B and 2‐N . Cyclic voltammetry (CV) studies showed that 2‐B undergoes a quasi‐reversible one‐electron reduction, which was confirmed by the synthesis of [K([2.2.2]crypt)][L(Cl)GaSbB[N(Dip)CH] 2 ] ([K([2.2.2]crypt)][ 2‐B ]) containing the stibanyl anion [ 2‐B ] − , which was shown to possess significant Sb−B multiple‐bonding character.