Date of Award

1982

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

The oxidation of indium(II) complexes In(,2)X(,6)('2-) with halogen Y(,2) yields the anionic halogeno mixed complexes InX(,3)Y('-). Similar oxidations of the indium(I) anions InX(,2)('-) furnish InX(,2)Y(,2)('-) complexes, all as salts with tetraalkylammonium cations. The far-infrared and Raman spectra establish that the anions are indeed the mononuclear mixed-ligand species. Similar reactions, in which the metal-metal bond in In(,2)X(,6)('2-) is cleaved with methyl halides MeX, afford MeInX(,3)('-)(X (NOT=) Y = Cl, Br, I). The mechanism of rupture of the metal-metal bond is discussed. ('115)In-NMR studies are reported for InX(,4)('-), In(,2)X(,6)('2-), InX(,3)Y('-), InX(,2)Y(,2)('-) and InX(,4)('-) in the presence of X('-) (X and Y as before) in various nonaqueous solvents. The results confirm and extend previous studies of the nonaqueous solution chemistry of these complexes. The macrocycles dibenzo-18-crown-6-ether and 1,4,8,11-tetraazacyclotetradecane form adducts with InX(,2) and InX(,3), but not with InX (X = Cl, Br, I). Vibrational spectroscopy shows that the products In(,2)X(,4)L (L = macrocycle) should be formulated as {InL}{InX(,4)}. With InX(,3) and dibenzo-18-crown-6-ether the spectra reveal the presence of InX(,4)('-) anions and linear InX(,2)('+) species. The reaction of cyclam and InX(,3) yields products formulated as {In(cyclam)(,2)}{InX(,4)}(,3). The neutral indium(II) compounds In(,2)X(,4)(Et(,3)P)(,2), In(,2)X(,4)(TMED)(,2) and In(,2)X(,4)(TMED)(,2)C(,6)H(,6) (X = Cl, Br; TMED = N,N,N',N'-tetramethylethylenediamine) have been prepared by the reaction of InX(,2) and donor in benzene or toluene. With several other neutral donors, and in all systems involving InCl(,2), decomposition to indium metal is the predominant process. Analysis of the vibrational spectra demonstrates that these structures involve X(,2)In-InX(,2) kernels. Slight revisions are proposed to previous discussions of the infrared spectra of In(,2)X(,6)('2-) anions. Several synthetic routes to prepare organoindium(II) derivatives are described. Such reactions invariably lead to production of indium metal. Possible mechanisms for this decomposition are discussed. A convenient method for the preparation of cyclopentadienylindium(I) is reported.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1982 .V537. Source: Dissertation Abstracts International, Volume: 43-03, Section: B, page: 0722. Thesis (Ph.D.)--University of Windsor (Canada), 1982.

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