Date of Award
Chemistry and Biochemistry
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Indium(I) halides (InX) dissolve in toluene containing certain neutral donor ligands below ca. 0(DEGREES)C. The simplest solute species in InBr-toluene-N,N,N',N'-tetramethylethylenediamine (tmen) is InBr.3tmen, but the solution slowly precipitates solid InBr. 1/2tmen. Disproportionation of InX occurs above 0(DEGREES)C, yielding indium metal and In('II) or In('III) complexes, depending on X and the neutral ligand. In solution, InX (X = Cl, Br, I) can oxidatively insert into the In('III)-Y bond of InY(,3) (Y = Br, I) in toluene-dichloromethane-tmen to give neutral tmen adducts of In(,2)XY(,3). Vibrational spectroscopy and n.m.r. studies suggest that the structures involve X(Y)In-InY(,2) kernels, and this was confirmed by the crystal structure determination of In(,2)Br(,3)I.2tmen. The evidence leads to a discussion of the InX-InY(,3)-base and InX(,2)-base systems as related processes. With InCl(,3), the product of reaction with InX is the bis-tmen adduct of Cl(X)InCH(,2)InCl(,2), which contains a methylene group bridging two indium atoms; the structure was confirmed by X-ray analysis in two cases (X = Cl, Br). In the course of this work we have observed that tmen reacts slowly with CH(,2)Cl(,2) to form 1,1,3,3-tetramethylimidazolidinium dichloride, a cyclic 5-membered diammonium cation; the reaction between InI and InCl(,3) gave, inter alia, the crystalline diiodide derivative of the cyclic cation as the CH(,2)Cl(,2) solvate, whose crystal structure is reported. The indium(I) halide species in solution oxidatively inserts into RM-MR bonded systems (M = O, S, Se, Co) in toluene (or CH(,2)Cl(,2))-pyridine (py). The products are generally of the type (RM)(,2)InX, obtained as the bis-pyridine adducts. Reaction does not occur for M = Sn, Pb, N, P, Te, Mn, Fe. The mechanism of such insertion processes is discussed; the donor and acceptor properties of both In('I) and M are important. The InX-benzoyl peroxide system gives rise to a series of products which suggest re-arrangement in solution following the insertion of InX into the O-O bond; the structure of one compound, dichloro(benzoato)bis(pyridine)indium(III), was confirmed by X-ray crystallography. The addition reaction between solutions of InX and alkyl halides (RX) gives adducts of RInX(,2). The crystal structures of two products, i.e., C(,2)H(,5)InX(,2).tmen (X = Br, I) are reported. . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of author.) UMIDept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1983 .P466. Source: Dissertation Abstracts International, Volume: 44-10, Section: B, page: 3076. Thesis (Ph.D.)--University of Windsor (Canada), 1983.
PEPPE, CLOVIS., "OXIDATIVE INSERTION REACTIONS OF NON-AQUEOUS SOLUTIONS OF INDIUM(I) HALIDES." (1983). Electronic Theses and Dissertations. 2974.