Showing papers in "Inorganic Chemistry in 1963"

Chelates of β-Diketones. V. Preparation and Properties of Chelates Containing Sterieally Hindered Ligands

Abstract: A number of metal chelates containing the anions of β-diketones as ligands have been prepared. Various synthetic procedures are described and physical characteristics are reported.

Spectroscopic Studies of the Complexes of Acrylonitrile and Acetonitrile with the Carbonyls of Chromium, Molybdenum, and Tungsten

Abstract: Infrared and proton magnetic resonance spectroscopic studies of acrylonitrile complexes of the carbonyls of Cr, Mo, and W are used to assign the geometrical isomerism and manner of attachment of the ligand in these derivatives. Similar studies are also reported for the acetonitrile derivatives, from which the acrylonitrile complexes have been obtained. Evidence is presented for attachment of acrylonitrile through the nitrogen lone-pair in (CH2CHCN)M( C0)s ( M = W) and (CHzCHCN)*M(C0)a (M = Cr, Mo, and W), which are among the first well characterized examples of this type of bonding for this ligand (heretofore assumed to attach to transition metals principally through the olefinic carbon-carbon bond). The trisubstituted complexes (CH?CHCN),M( CO)3 ( M = Mo and W) appear to have the CZ, (trans) geometry, even though they were prepared by displacement of the ligand from C3" ( c i s ) acetonitrile complexes. The acrylonitrile is attached through the olefinic carbon-carbon bond in these derivatives.

Chemistry of decaborane-phosphorus compounds. iv. monomeric, oligomeric and cyclic phosphino carboranes

Abstract: : Dilithiocarborane, B10H10C2Li2, was allowed to react with chlorophosphines containing one, two, and three chlorine atoms. (C6H5)2PCl a C6H5PCl2 gave the expected disubstituted compounds, B10H10C2 P(C6H5)2 2 and B10H10C2(C6H5P. Cl)2, respectively. B10H10C2Li2 and PCl3, how ever, formed a compound having two phosphorus atoms and two carborane nuclei in a six membered ring. This unique ring system also arose from the reaction of B10H10C2Li2 with B10H10C2 (C6H5P.Cl)2. Subsequent reactions of such mole cules with ammonia and NaN3 are described. The cyclic bis-azide, (B10H10C2P.N3)2, and p P(C6H5)2 2C6H4 reacted to form a PNP bonded oligomer.

Amides as ligands. i. metallic complexes of n,n-dimethylacetamide

Abstract: The preparation of 26 metallic complexes of 14 different metals with N,N- dimethylacetamide (DMA) is reported. The complexes were characterized by their melting points, infrared spectra in the 2 to 15 mu region, electrical conductance in DMA, and magnetic moments. The infrared spectra suggest that coordination through the oxygen of DMA occurs for all the metals investigated. In most instances, the complexes contain fewer moles of DMA than the maximum coordination number of the metal, indicating coordination by halide ion and/or water. (auth)

Direct synthesis of complex metal hydrides

Abstract: The direct synthesis of NaAlH/sub 4/, LiAlH/sub 4/, KAlH/sub 4/, and CsAlH/sub 4/ from the elements was accomplished. The reaction of the alkali metal, aluminum, and hydrogen proceeds at moderate temperatures and pressures to produce nearly quantitative yields of high purity alkali metal aluminum hydride. The method affords a convenient laboratory as well as commercial route to NaAlH/ sub 4/ and LiAlH/sub 4/. The effects of temperature, pressure, solvent, and other variables were determined. A mechanism for the reaction is discussed. The reaction of sodium, aluminum, hydrogen, and olefins to produce compounds of the structure NaAlR/sub n/H/sub 4-n/ also was accomplished. A promising route to unetherated LiAlH/sub 4/ was found. The route involves the metathetical reaction of NaAlH/sub 4/ and LiCl in diethyl ether. The effects of solvents and temperature on yield of LiAlH/sub 4/ were investigated. A convenient method of isolation and purification of LiAlH/sub 4/ was developed which preduces LiAlH/sub 4/ in approximately 99% purity. (auth)