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Anionic, Four-co-ordinate, Ten-electron Bismuth Complexes: Aspects of Synthesis, Structure and Bonding

DOI: 10.1039/DT9920003515

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3515 - 3524 (1992)

Update date:2022-08-02

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Authors:

Clegg, WilliamClegg, William

Compton, Neville A.Compton, Neville A.

Errington, R. JohnErrington, R. John

Fisher, George A.Fisher, George A.

Hockless, David C. R.Hockless, David C. R.

et al.et al.

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Article abstract of DOI:10.1039/DT9920003515

The reaction between 2> 1 and 1 equivalent of Cl afforded the ionic complex 2> 2.The (1+) salt, 2> 3, was prepared similarly.An analogous bromide derivative, 2> 4, was prepared from the reaction between 2> 5 and Br.The reaction between 2> 7 and 1 equivalent of Cl afforded the complex 2> 8; that between Cl and 7 afforded 2> 9.In tetrahydrofuran (thf) solution some degree of dissociation of (1-) is observed for 8 and 9.The bromide complexes 2> 10 and n4>2> 11 were prepared from the reactions between 2> 12 and 1 equivalent of Br and n4>Br respectively.The tungsten complexes 2> 13 and 2> 14 were similarly prepared.Spectroscopic data for the complexes > 16 and > 17 are also presented.The structures of compounds 2, 8, 9 (as a thf solvate) and 13 were determined by X-ray crystallography.The structures of all of the compounds comprise a four-co-ordinate bismuth centre bonded to two chlorine atoms and two MLn fragments.The precise co-ordination geometries, however, vary from close to an idealised equatorially-vacant trigonal bipyramid (disphenoidal), 2 and 9, with axial chlorines and equatorial metal centres, to nearly tetrahedral, 8 and 13.These results are incorporated into a general discussion of the structures found for AB4E complexes, i.e. four-co-ordinate with ten valence electrons, and some ideas are advanced on possible electronic factors which determine the particular geometry adopted.

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