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The University of Southampton
Chemistry

Research project: Levason: Coordination Chemistry of Early Transition Metals and Lanthanides

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Early transition metals in medium or high oxidation states are typical hard acceptors which preferentially bind hard donor O- or N- based ligands.

However, with suitable synthetic approaches complexes with soft ligands such as phosphines, arsines or thio- or seleo-ethers can be obtained. The complexes with soft donor ligands are often extremely moisture sensitive and highly reactive, but promote a significantly different chemistry to hard donor analogues. In this research programe both hard and soft ligand types are used to explore the differences in resulting structures and reactivities.

Six- and eight-coordinate thio- and seleno-ether complexes of Ti(IV), Zr(IV), Hf(IV) have been studied in detail and how the ligand architecture controls the metal coordination number elucidated. Similar studies using chelating diphosphine and diarsine ligands have produced 8-coordinate Zr(IV), Hf(IV) and Ti(IV) complexes, and more recently Mo(VI), W(VI), V(V) and (IV) analogue shave been obtained. Currently the work is being extended to the metal fluoride systems, where the very different electronic properties conferred by the electronegative fluorine ligands produce very different coordination chemistry, and sometimes result in fluorination of the ligands. Thio- and seleno-ether, and seleno- (RSe-) and tellurolate (RTe-)of Zr, Hf, Nb and Ta halides are being explored as single source CVD precursors to MS2 and MSe2 films.

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(1,10-phenathroline)

Related research groups

Functional Inorganic, Materials and Supramolecular Chemistry
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