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trans-Influence in Heavy Main Group Compounds: A Case Study on Tris(pyrazolyl)borate Bismuth Complexes

Balasubramaniam, S and Kumar, S and Andrews, AP and Jemmis, ED and Venugopal, A (2020) trans-Influence in Heavy Main Group Compounds: A Case Study on Tris(pyrazolyl)borate Bismuth Complexes. In: European Journal of Inorganic Chemistry, 2020 (26). pp. 2530-2536.

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Official URL: https://doi.org/10.1002/ejic.202000314


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 �-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)32+ in addition to the recently reported TpMe2BiCl2, TpMe2Bi2+, TpMe2Bi2Bi3Cl13 and KTpMe2Bi(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. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Item Type: Journal Article
Publication: European Journal of Inorganic Chemistry
Publisher: Wiley-VCH Verlag
Additional Information: Copyright of this article belongs to Wiley-VCH Verlag
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 01 Apr 2021 05:48
Last Modified: 01 Apr 2021 05:48
URI: http://eprints.iisc.ac.in/id/eprint/65525

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