Abstract
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(TpMe2), a C3v 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 TpMe2Bi species by accessing five new moieties [TpMe2BiCl3]–, (TpMe2)2Bi+, TpMe2BiCl(OTf), TpMe2Bi(OTf)2 and [TpMe2Bi(solvent)3]2+ in addition to the recently reported TpMe2BiCl2, TpMe2Bi2+, [TpMe2Bi]2[Bi3Cl13] and K[TpMe2Bi(OTf)3]. Analysis of structures by X‐ray crystallographic studies and computational analysis on TpMe2Bi species establish the variation of trans‐influence and demonstrate a continuum in bonding of TpMe2 to bismuth correlating with the degree of nucleophilicity of the trans‐ligands.
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