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trans ‐Influence in Heavy Main Group Compounds: A Case Study on Tris(pyrazolyl)borate Bismuth Complexes
Author(s) -
Balasubramaniam Selvakumar,
Kumar Sandeep,
Andrews Alex P.,
Jemmis Eluvathingal D.,
Venugopal Ajay
Publication year - 2020
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.202000314
Subject(s) - chemistry , nucleophile , electrophile , bismuth , lewis acids and bases , main group element , ligand (biochemistry) , stereochemistry , boron , medicinal chemistry , crystallography , catalysis , transition metal , organic chemistry , biochemistry , receptor
Compounds of heavy main group elements possessing polarized primary bonds exhibit trans ‐influence. The extent of secondary interactions at the electrophilic sites trans to the primary bonds provides an understanding on the Lewis acidity exhibited by the main group element center, thus forming the basis for designing Lewis acid catalysts. Hydridotris(3,5‐dimethylpyrazolyl)borate(Tp Me2 ), a C 3 v symmetric tridentate σ‐donor ligand, offers an opportunity to explore trans ‐influence in Bi(III) compounds in the presence of donor ligands with varying nucleophilicity. We have examined a series of Tp Me2 Bi species by accessing five new moieties [Tp Me2 BiCl 3 ] – , (Tp Me2 ) 2 Bi + , Tp Me2 BiCl(OTf), Tp Me2 Bi(OTf) 2 and [Tp Me2 Bi(solvent) 3 ] 2+ in addition to the recently reported Tp Me2 BiCl 2 , Tp Me2 Bi 2+ , [Tp Me2 Bi] 2 [Bi 3 Cl 13 ] and K[Tp Me2 Bi(OTf) 3 ]. Analysis of structures by X‐ray crystallographic studies and computational analysis on Tp Me2 Bi species establish the variation of trans ‐influence and demonstrate a continuum in bonding of Tp Me2 to bismuth correlating with the degree of nucleophilicity of the trans ‐ligands.