| Popis: |
This thesis describes a broad study of the co-ordination chemistry and reactions of indium trihalides and trialkyls. Particular emphasis has been placed upon indium compounds which also contain phosphorus. A detailed study of the 1:1 complexes formed between indium triiodide and several phosphine ligands is described. X-ray crystallographic studies showed that these complexes are tetrahedral monomers in the solid state. This is the first conclusive proof that indium triiodide will form monomeric tetrahedral complexes. N.m.r. studies have also been carried out on these complexes. Also described are the results of X -ray diffraction studies on two other phosphine complexes. InCI3(PMe3)2 and (InI3)2(Diphos)3. The latter complex is the first example of a trigonal bipyramidal structure that has been reponed for any indium triiodide complex. The reactions between methyllithium and two indium triiodidephosphine complexes are described. This proved to be a useful method for preparing methylated derivatives of these complexes. The reactions between indium triiodide and LiPBut2 are also described. Three equivalents of this reagent yielded In(PBut2)3, which was shown by X-ray crystallography to be an example of a rare monomeric three coordinate indium compound. Also described in this thesis are the preparations of several novel organoindium derivatives by the reaction of either trimethyl- or triethylindium with acidic compounds containing protonic hydrogens. Where possible, structures of the products of these reactions have been deduced. One of these compounds [(Et2InPBut2)2] was studied in greater detail and in the solid state it was shown by X -ray crystallography to be dimeric. Its thermal decomposition was also studied in view of the possible relevance of such compounds to the preparation of indium phosphide. Possible decomposition pathways are discussed. |
