Organo-gallium/indium chalcogenide complexes of copper(I): molecular structures and thermal decomposition to ternary semiconductors.

Several organo-gallium/indium chalcogenide complexes of copper(I), stabilized by trialkylphosphines, were isolated, structurally characterized by using single-crystal X-ray diffraction, and investigated in thermolysis experiments. The syntheses with [E(Me3Si)2] (E=S, Se) as a starting material and a chalcogen source involve the elimination of volatile silyl acetate, silyl ethers, and methane from copper(I) acetate, and Group 13 metal trimethyl compounds, respectively. Chalcogenide complexes, according to the general formulas [(R3PCu)4(MeM)4E6] (1-6) and [(R3PCu)6(MeM)4M4S13] (7-9; with R=alkyl and M=Ga, In), and mixed chalcogenide-phenylchalcogenolate complexes [(iPr3PCuEPh)3(MeGaE)4] (10, 11) were isolated.

Tetranuclear organometallic complexes based on 1,2-ethanedithiolate ligands as potential precursors for CuMS2 (M = Ga, In).

The synthesis and characterization of a series of homologous tetranuclear complexes [((i)Pr3PCu)2(MR2)2(SCH2CH2S)2] (MR2 = GaMe2 (2), GaEt2 (3), Ga(i)Pr2 (4), Ga(n)Bu2 (5) and InMe2 (6), InEt2 (7), In(i)Pr2 (8), In(n)Bu2 (9)) and of related compounds [((i)Pr3PCu)3(MR2)(SCH2CH2S)2] (MR2 = GaMe2 (10), GaEt2 (11), Ga(i)Pr2 (12), Ga(n)Bu2 (13) and InMe2 (14), InEt2 (15), In(i)Pr2 (16), In(n)Bu2 (17)) are presented. The molecular structures of these were determined by single crystal X-ray diffraction. Thermolysis processes of all the representatives of 2-9 were investigated by simultaneous thermal analysis and thermal decomposition in a nitrogen atmosphere in a quartz glass tube.

New organometallic single-source precursors for CuGaS(2)-polytypism in gallite nanocrystals obtained by thermolysis.

The complex [((i)Pr(3)PCu)(2)(Me(2)Ga)(2)(SCH(2)CH(2)S)(2)] (4) was synthesized from trimethylgallium, [((i)Pr(3)PCu)(4)(SCH(2)CH(2)S)(2)] (1) and ethanedithiol by elimination of methane. The related monomethyl compound [((i)Pr(3)PCu)(2)(MeGaSPh)(2)(SCH(2)CH(2)S)(2)] (5) has been prepared from [((i)Pr(3)PCuSPh)(3)] (2) and [(MeGaSCH(2)CH(2)S)(2)] (3) by a ligand exchange reaction in tetrahydrofuran solution. The molecular structures of 1 and 3-5 were determined by single crystal X-ray diffraction.

Trialkylphosphine-stabilized copper(I) gallium(III) phenylchalcogenolate complexes: crystal structures and generation of ternary semiconductors by thermolysis.

A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R(3)P)(m)Cu(n)Me(2-x)Ga(EPh)(n+x+1)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te; x = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis.

Trialkylphosphine-stabilized copper(I) phenylchalcogenolate complexes--crystal structures and copper-chalcogenolate bonding.

A series of trialkylphosphine-stabilized copper(I) phenylchalcogenolate complexes [(R(3)P)(m)(CuEPh)(n)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te) has been prepared and structurally characterized by X-ray diffraction. Structures were found to be mono-, di-, tri-, tetra-, hexa-, hepta-, or decanuclear, depending mainly on size and amount of phosphine ligand. Several structural details were observed, including unusually long Cu-E bonds or secondary Cu-E connections, μ(4)-bridging, and planar bridging chalcogenolate ligands.

Integration of electron density and molecular orbital techniques to reveal questionable bonds: the test case of the direct Fe-Fe bond in Fe2(CO)9.

The article illustrates the advantages of partitioning the total electron density rho(rb), its Laplacian (inverted Delta)2 rho(rb), and the energy density H(rb) in terms of orbital components. By calculating the contributions of the mathematically constructed molecular orbitals to the measurable electron density, it is possible to quantify the bonding or antibonding character of each MO. This strategy is exploited to review the controversial existence of direct Fe-Fe bonding in the triply bridged Fe2(CO)9 system.

Orbital contributions to the molecular charge and energy density distributions in Co2(CO)8.

For Co2(CO)8, the representative of a whole class of bridged cobalt complexes, the 18-electron rule predicts a direct metal-metal bond in addition to the metal-bridge bonds. By intuition, this bond should have bent-bond character. However, it is well-known from charge density analyses that no bond critical point exists in the corresponding spatial region.