Controlling the oxidation state of arsenic in cyclic arsenic cations.

Reduction of AsCl3 with SnCl2, followed by treatment of the "AsCl" with a 1,4-diimine results in electron transfer and formation of an arsenic(III) salt, while treatment of this arsenic(I) reagent or AsI3 with an alpha,alpha'-diiminopyridine ligand forms an arsenic(I) salt.

Direct reactions of tellurium tetrahalides with chelating nitrogen ligands. Trapping of TeL2 by a 1,2-bis(arylimino)acenaphthene (aryl-BIAN) ligand and C-H activation of an alpha,alpha'-diiminopyridine (DIMPY) ligand.

The reaction of TeI4 with the 2,6-diisopropylphenyl-substituted 1,2-bis(arylimino)acenaphthene ligand dpp-BIAN results in two-electron reduction of tellurium and formation of the complex (dpp-BIAN)TeI2, while treatment of TeCl4 with the alpha,alpha'-diiminopyridine ligand dpp-DIMPY causes C-H activation of an imino methyl group.

A single-bonded cationic terminal borylene complex.

The cationic terminal borylene complex [(eta5-C5H5)(CO)2FeB(eta5-C5Me5)][AlCl4] has been isolated from the reaction of [(eta5-C5H5)(CO)2FeB(Cl)(eta1-C5Me5)] with AlCl3 and on the basis of X-ray crystallographic data, spectroscopic data and a DFT calculation it is concluded that the B-->Fe bond order is one.

An N,N'-chelated phosphenium cation supported by a beta-diketiminate ligand.

The first example of a phosphenium cation supported by N,N'-chelation of a beta-diketiminate ligand has been prepared and structurally characterized.

N,C-bonded beta-diketiminato phosphenium cations.

The first examples of N,C-bonded beta-diketiminato phosphenium cations have been isolated as their triflate or tetrachloroaluminate salts, both of which have been structurally characterized.

Facile routes to alkyl-BIAN ligands.

The Alkyl-BIAN ligands tert-Butyl-BIAN and 1-Adamantyl-BIAN have been synthesized and their structures have been determined by single-crystal X-ray diffraction along with that of the ZnCl2 complex of tert-Butyl-BIAN.

Gallium-containing conducting metallopolymers which display chemically tunable reactivity for the growth of Ga2S3 semiconducting nanoparticles.

Electropolymerization of novel gallium Schiff-base complexes results in conducting metallopolymers containing either coordinatively saturated or unsaturated gallium metal centers. Depending on the chemical coordination of the metal centers, the embedded metal ions can act as seed points for the direct growth of size-controlled gallium sulfide nanoparticles in a conducting polymer, yielding a hybrid electronic material.

Charge separation by ditopic complexation in the solid state: molecular structure of {Ph2(I)SnCH2Sn(Ph)(I)CH2-[16]-crown-5}.NaF.CH3OH.

An intramolecular O-H-F hydrogen bridge involving a methanol molecule provides communication between the strongly separated sodium cation and fluoride anion in sodium fluoride that is, for the first time and despite its high lattice energy, ditopically complexed by an organotin-substituted crown ether.

Synthesis and structures of boron dihalides supported by the C(6)F(5)-substituted beta-diketiminate ligand [HC(CMe)(2)(NC(6)F(5))(2)](-).

The new boron dihalides of the type [HC(CMe)(2)(NC(6)F(5))(2)]BX(2) (X = Cl, Br, I) have been prepared and characterized by single-crystal X-ray diffraction. Of the various synthetic approaches explored, the best method in terms of yield and product purity involves the silylhalide elimination reaction of the silylated iminoamine [HC(CMe)(2)(NC(6)F(5))(N{SiMe(3)}C(6)F(5))] with BX(3). Chloroborenium salt [HC(CMe)(2)(NC(6)F(5))(2)BCl][AlCl(4)] was prepared by treatment of [HC(CMe)(2)(NC(6)F(5))(2)]BCl(2) with AlCl(3) in CH(2)Cl(2) solution. This salt was also structurally authenticated and represents the first such data for a beta-diketiminate-supported haloborenium cation.

Solubilizing sodium fluoride in acetonitrile: synthesis, molecular structure, and complexation behavior of bis(organostannyl)methyl-substituted crown ethers.

The synthesis of the crown-ether-substituted bis(organostannyl)methanes Ph(3)SnCH(2)Sn(Ph(2))-CH(2)-[16]crown-5 (1) and Ph(2)ISnCH(2)Sn(I)(Ph)-CH(2)-[16]crown-5 (2) is reported. Both compounds have been characterized by elemental analyses, (1)H, (13)C, (19)F, and (119)Sn NMR spectroscopy, and in the case of compound 2 also by electrospray ionization mass spectrometry. Single-crystal X-ray diffraction analysis revealed for the aqua complex 2.H(2)O trigonal-bipyramidal-configured tin atoms with intramolecular Sn(1)-O(1) and Sn(2)-O(1W) distances of 2.555(2) and 2.440(3) A, respectively. The water molecule is trapped in a sandwich-like fashion between the crown ether oxygen atoms O(2) and O(4) and the Sn(2) atom. NMR spectroscopy unambiguously proved the ability of compound 2 in acetonitrile to overcome the high lattice energy of sodium fluoride and to complex the latter under charge separation.

One-step redox route to N-heterocyclic phosphenium ions.

One-step reactions of the appropriate N-alkyl-, N-cycloalkyl-, and N-aryl-substituted alpha-diimines with PI3 afforded >80% yields of the triiodide salts of the following N-heterocyclic phosphenium ions, [(R1NC(R2)C(R2)NR1)P]+: 3 (R1 = t-Bu; R2 = H); 4 (R1 = 2,6-i-Pr2C6H3; R2 = H), 5 (R1 = Mes; R2 = H), 6 (R1 = 2,6-i-Pr2C6H3; R2 = H), and 7 (R1 = cyclohexyl; R2 = H). Treatment of 3 and 6 with NaB(C6H5)4 resulted in virtually quantitative yields of the corresponding [B(C6H5)4]- salts 8 and 9, respectively. The X-ray crystal structures of 3 and 5-9 were determined.

Capture of phosphorus(I) and arsenic(I) moieties by a 1,2-bis(arylimino)acenaphthene (aryl-BIAN) ligand. A case of intramolecular charge transfer.

The reaction of PCl3 with SnCl2 in THF solution, followed by treatment with dpp-BIAN (dpp = 2,6-i-Pr2C6H3), affords the phosphenium complex [(dpp-BIAN)P][SnCl5.THF]. The 31P chemical shift (delta 232.5) and the metrical parameters from a single-crystal X-ray diffraction study indicate that the oxidation state of phosphorus in this compound is +3. A similar conclusion was reached regarding the phosphorus oxidation state in [(dpp-BIAN)P][I3], which was prepared via the reaction of dpp-BIAN with PI3 in CH2Cl2 solution. The arsenium salt [(dpp-BIAN)As][SnCl5.THF] was prepared by treatment of AsCl3 with SnCl2 in THF solution, followed by the addition of dpp-BIAN. The X-ray crystal structure of this salt was determined, and the pattern of bond distances and angles indicates that arsenic is present in the +3 oxidation state.

Complexes of 1,2-bis(aryl-imino)acenaphthene (Ar-BIAN) ligands with some heavy p-block elements.

The new Ar-BIAN complexes [(mes-BIAN)InCl(3)(THF)] (1), [(mes-BIAN)(2)Tl][PF(6)] (2), [(dipp-BIAN)SnCl(4)] (3), [(dipp-BIAN)SbCl(3)] (4), [(dipp-BIAN)BiCl(3)] (5) and [(mes-BIAN)BiCl(3)] (6) have been prepared by treatment of the neutral mes- and dipp-substituted BIAN ligands with the p-block reagents InCl(3), TlPF(6), SnCl(4), SbCl(3), and BiCl(3). The molecular structures of complexes 1-6 have been determined by single-crystal X-ray diffraction methods. However, only the atom connectivity was established for 5.