103349-18-4Relevant academic research and scientific papers
trans-Influence in Heavy Main Group Compounds: A Case Study on Tris(pyrazolyl)borate Bismuth Complexes
Balasubramaniam, Selvakumar,Kumar, Sandeep,Andrews, Alex P.,Jemmis, Eluvathingal D.,Venugopal, Ajay
, p. 2530 - 2536 (2020/05/18)
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.
Arene Complexes with an Inverse Sandwich Structure: The 1:2 Complexes of Hexamethylbenzene with SbCl3, SbBr3, BiCl3, and BiBr3
Schmidbaur, Hubert,Nowak, Reinhold,Schier, Annette,Wallis, Julian M.,Huber, Brigitte,Mueller, Gerhard
, p. 1829 - 1836 (2007/10/02)
Hexamethylbenzene forms stable 1:2 complexes with SbCl3, SbBr3, BiCl3 and BiBr3 of the type X3E*C6Me6*EX3 (1-4) with an inverse sandwich structure.Crystals of the colourless antimony compounds and of the yellow bismuth compounds are isotypic (tetragonal, space group P42/nnm).The structures are built up of tetrameric units E4X12, which are crosslinked by double-sided arene coordination at each metal center E with four other tetramers, to give a three-dimensional organometallic polymer.While the Bi atoms in 3 and 4 are, to a first approximation, η6 coordinated to the aromatic hydrocarbon from both sides, the Sb atoms in 1 and 2 are shifted sidewise in opposite directions as projected onto the arene plane.The positions of the antimony atoms as well as those of the associated bridging halogen atoms in the lattice can be accounted for by a 50:50 disorder relative to the crystallographic symmetry elements.Isotypic complexes with pentamethylbenzene have also been obtained.
