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From Dibismuthenes to Three‐ and Two‐Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC 3 N Rings through a Combined Experimental and Theoretical Study
Author(s) -
Vránová Iva,
Alonso Mercedes,
Lo Rabindranath,
Sedlák Robert,
Jambor Roman,
Růžička Aleš,
Proft Frank De,
Hobza Pavel,
Dostál Libor
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502724
Subject(s) - bismuth , chelation , ligand (biochemistry) , lone pair , delocalized electron , aromaticity , chemistry , ring (chemistry) , intramolecular force , monomer , crystallography , stereochemistry , molecule , inorganic chemistry , organic chemistry , polymer , biochemistry , receptor
The reduction of N,C,N‐chelated bismuth chlorides [C 6 H 3 ‐2,6‐(CHNR) 2 ]BiCl 2 [where R= t Bu ( 1 ), 2′,6′‐Me 2 C 6 H 3 ( 2 ), or 4′‐Me 2 NC 6 H 4 ( 3 )] or N,C‐chelated analogues [C 6 H 2 ‐2‐(CHN‐2′,6′‐ i Pr 2 C 6 H 3 )‐4,6‐( t Bu) 2 ]BiCl 2 ( 4 ) and [C 6 H 2 ‐2‐(CH 2 NEt 2 )‐4,6‐( t Bu) 2 ]BiCl 2 ( 5 ) is reported. Reduction of compounds 1 – 3 gave monomeric N,C,N‐chelated bismuthinidenes [C 6 H 3 ‐2,6‐(CHNR) 2 ]Bi [where R= t Bu ( 6 ), 2′,6′‐Me 2 C 6 H 3 ( 7 ) or 4′‐Me 2 NC 6 H 4 ( 8 )]. Similarly, the reduction of 4 led to the isolation of the compound [C 6 H 2 ‐2‐(CHN‐2′,6′‐ i Pr 2 C 6 H 3 )‐4,6‐( t Bu) 2 ]Bi ( 9 ) as an unprecedented two‐coordinated bismuthinidene that has been structurally characterized. In contrast, the dibismuthene {[C 6 H 2 ‐2‐(CH 2 NEt 2 )‐4,6‐( t Bu) 2 ]Bi} 2 ( 10 ) was obtained by the reduction of 5 . Compounds 6 – 10 were characterized by using 1 H and 13 C NMR spectroscopy and their structures, except for 7 , were determined with the help of single‐crystal X‐ray diffraction analysis. It is clear that the structure of the reduced products (bismuthinidene versus dibismuthene) is ligand‐dependent and particularly influenced by the strength of the N→Bi intramolecular interaction(s). Therefore, a theoretical survey describing the bonding situation in the studied compounds and related bismuth(I) systems is included. Importantly, we found that the C 3 NBi chelating ring in the two‐coordinated bismuthinidene 9 exhibits significant aromatic character by delocalization of the bismuth lone pair.