Journal of the Chemical Society, Dalton Transactions p. 1163 - 1172 (1995)
Update date:2022-08-03
Topics:
Farrugia, Louis J.
Lawlor, Fiona J.
Norman, Nicholas C.
The reaction between Bi(SC6F5)3 1 and SPPh3 afforded crystals of a bismuth centre bonded to three SC6F5 groups and the sulfur atom of a SPPh3 ligand such that the co-ordination geometry is disphenoidal with the SPPh3 ligand trans to one thiolate group.An additional intermolecular interaction is also present due to a weakly bridging thiolate sulfur which results in a centrosymmetric dimer with each bismuth centre having square-based pyramidal five-co-ordination.A similar structure was observed for the anion in the ionic complex a disphenoidal geometry with an axial thiolate and N-bonded thiocyanate ligand which also bridges between two centrosymmetrically related bismuth centres giving a structure similar to 5.The reaction between 1 and either OPPh3, hmpa (hexamethylphosphoramide) or dmpu (N,N'-dimethylpropyleneurea) afforded the bis(ligand) complexes a five-co-ordinate, square-based pyramidal geometry around the bismuth centre with one thiolate in the apical site and the two ligands in a cis configuration in the basal plane each trans to a basal thiolate.The reaction between 1 and N,N'-dimethylthiourea, S=C(NHMe)2, afforded the tris(ligand) complex a six-co-ordinate complex with a geometry close to that of a regular octahedron with the three thiolates and three thiourea ligands both having fac configurations.The structures are discussed in terms of the SC6F5 group having properties analogous to chloride, and hence being a pseudohalide, and also in terms of ligand co-ordination occuring through the thiolate Bi-S ?* orbitals.
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