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The University of Southampton

Research project: Levason: Chemistry of Bi- and Polydentate Antimony and Bismuth Ligands

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Although often assumed to be simply "weaker donor pseudo-phosphines", our recent studies have shown that antimony ligands are fundamentally different from their lighter analogues, their weaker donor power and smaller cone angles leading to different stoichiometries, higher coordination numbers, unusual isomers and less dissociation in solution.

[Rh(CO){Ph2Sb(CH2)3SbPh2}]2]+ cationPrevious work has included studies of distibinomethanes (R2SbCH2SbR2), the only known complexes of a tridentate stibine MeC(CH2SbPh2)3, and of the first bidentate dibismuthine p-Ph2BiC6H4BiPh2. New routes to distibines have been developed based upon diGrignard reagents and these have given o,m and p-xylyl-C6H4(CH2SbMe2)2 and m- and p-phenylene distibines C6H4(SbMe2)2 in unprecedentedly high yields. These ligands have been complexed with a variety of metal carbonyl substrates and with metal halides in Groups 9-11. The first series of organoplatinum(II) and (IV) and organorhodium(I) and organoiridium(I) complexes with distibines have been characterised. In current work we have prepared a range of chiral distibines, and their complexes with Mo(0), Pt(II) and Rh(I), and their catalytic properties are under investigation. The development of routes to polydentate and macrocyclic stibines is also a current target. Future research will include the completely unexplored area of early transition metal stibines. Under a very recently awarded EPSRC grant the synthesis of dibismuthines, their metal complexes and evaluation of slected complexes as precursors to bismuth-alloy thin films will be undertaken.

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[Rh(CO){Ph2Sb(CH2)3SbPh2}]2]+ cation

Related research groups

Functional Inorganic, Materials and Supramolecular Chemistry
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