Lewis base complexes of methyldihalobismuthines BiMeX2 (X = Cl or Br)

Benjamin, Sophie L., Levason, William, Reid, Gillian, Rogers, Michael C. and Warr, Robert P. (2012) Lewis base complexes of methyldihalobismuthines BiMeX2 (X = Cl or Br). Journal of Organometallic Chemistry, 708-709, 106-111. (doi:10.1016/j.jorganchem.2012.02.030).


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Methyldihalobismuthines, BiMeX2 (X = Cl or Br) prepared from MeLi and a stoichiometric amount of BiX3 in thf, react with 1,10-phenanthroline, 2,2′-bipyridyl or Me2NCH2CH2NMe2 (L−L) in thf or MeCN to give [BiMeX2(L−L)], which are poorly soluble in non-polar solvents. X-Ray structures of [BiMeBr2(L−L)] and of [BiMeCl2(Me2NCH2CH2NMe2)] show discrete square pyramidal molecules with apical methyl groups, and no intermolecular contacts within the sum of the appropriate Van der Waals radii. The structure of BiMe2Br is a 1-D polymer chain with bromine bridges containing a pseudo-trigonal bipyramidal geometry at bismuth. The reactions of BiMe2X with the bidentate N-donor ligands result in disproportionation to also form [BiMeX2(L–L)]. An unusual [BiMeBr4]2− anion in the salt [Li(H2O)(1,10-phen)2][Li(1,10-phen)2(μ-Br)BiMeBr3]·thf, was isolated as a by-product and shows a Li−Br−Bi bridge to one of the Li cations. BiMe2Br disproportionates on reaction with [M(CO)5(thf)] (M = Cr or W) to form [M(CO)5(BiMe3)].

Item Type: Article
ISSNs: 0022-328X (print)
0022-328X (electronic)
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Natural and Environmental Sciences > Chemistry
ePrint ID: 337022
Date Deposited: 16 Apr 2012 12:57
Last Modified: 28 Mar 2014 15:25
Research Funder: EPSRC
Dibismuthines: synthesis, metal complexes and evaluation as precursors for Bi alloy films
Funded by: EPSRC (EP/F038763/1)
Led by: William Levason
26 August 2008 to 25 December 2010
URI: http://eprints.soton.ac.uk/id/eprint/337022

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