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• W1493820748 abstract "This thesis describes a study of several aspects of the organometallic chemistry ofaluminium, gallium and indium.A study has been carried out on the products obtained from the reactions oftrimethyl- and triethyl-metal derivatives of aluminium, gallium and indium with amidines.The compounds [~M(L)] [L = amidinato (R'NCR''NR'); R' = aryl; = H, Me, Ph],[RM(PhNCRNPh)2]' and [M(PhNCRNPh)3](M = Al, R = Me; M = Ga, In; R = Me, Et;R = Me, Ph) have been isolated from the reactions of the appropriate trialkyl-metalderivative with 1, 2 and 3 moles of amidine [R'N(H)CR''NR'] respectively. The compoundshave been fully characterised, and mass spectroscopic data indicate that the compoundsexist as monomers in the gas phase. An X-ray crystallographic study was carried out on[Me2In(PhNCPhNPh)]. It was found to be monomeric and the ligand is attached in abidentate chelating manner. X-ray crystallographic studies on [RM(PhNCPhNPh)2] (M =Al, Ga, R = Me; M = In, R = Et) and [EtGa(PhNCMeNPh)2] reveal monomeric structuresand the presence of chelating amidinato ligands with highly distorted trigonal bipyramidalco-ordination at the metal centre. Cleavage of the metal-alkyl bond in some of thesedialkyl- and monoalkyl-metal derivatives on photolysis in the presence of a spin trappingagent was demonstrated using E.S.R. spectroscopy. An X-ray crystallographic study on[In(PhNCPhNPh)3] shows a monomeric structure in which the metal centre is six coordinateand the amidinato ligands are bound in a bidentate chelating manner. Some datahave been obtained on the thermal decomposition products of the metal-amidinatocomplexes in view of their potential use as III-V semiconductor precursors.The reactions of the simple N,N'-unsubstituted amidine ligands, butyramidine andtrifluoroacetamidine with Me3Ga have been investigated. The former amidine,[NH2CButNH], gave the dimethylgallium-butyramidinato compound and massspectroscopic data indicate that this compound is oligomeric and exists as both a dimer andmonomer in the gas phase. The latter amidine, [NH2CCF3NH], underwent a condensationreaction in the presence of M~Ga to form the complex [Me2Ga{HNC(CF3)NC(CF3)NH}].The molecular structure of this complex was determined by X-ray crystallography. It wasfound to consist of a planar six-membered metallocycle containing the N,N'-chelatingtrifluoroimidoyltrifluoracetamidinato ligand and a distorted tetrahedral co-ordinationenvironment around the metal.Several new indium(III) tetraaza-macrocycle complexes have been prepared usingthe unsaturated ligand 5,7,12, 14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine[H2tmtaa].The molecule structures of the compounds [XIn(tmtaa)] (X = Et, Cp, Cl) havebeen determined by X-ray crystallography. In each case, the structure consists of an InXfragment bonded to the four nitrogen atoms of the macrocyclic ligand. These structuresprovide unusual examples of indium in a five co-ordinate square based pyramidal coordinationgeometry in which the indium is centrally bound above the N4 plane of themacrocycle. The effects of change of both metal size and axial ligand on the moleculargeometry of these types of complex have been discussed in detail." @default.
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• W1493820748 date "1996-01-01" @default.
• W1493820748 modified "2023-09-24" @default.
• W1493820748 title "A study of the organometallic chemistry of aluminium, gallium and idium" @default.
• W1493820748 hasPublicationYear "1996" @default.
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