P. A. Petrov

SYNTHESIS OF ACETYLENIC TELLURIDES BY THE IODOMETHANE-INDUCED REACTION OF DIALKYL DITELLURIDES WITH PHENYLACETYLENE

Abstract Interaction of dialkyl ditellurides with phenylacetylene under phase transfer conditions occurs only in the presence of iodomethane giving rise to alkyl phenylethynyl tellurides in high yield. These compounds can also be obtained from alkyltellurenyl iodides and phenylacetylene under the same conditions.

Synthesis and structure of the cluster Fe2Mo2(μ3-Se)(μ3-AsMe)(μ3-Co)(μ-Co)(Co)5(η5-Cp)2

The reaction of (Et4N)2[Fe3(μ3-Se)(Co)9] with MeAsI2 afforded the [Fe3(μ3-Se)(μ3-AsMe)(Co)9] cluster, which was characterized by1H NMR and IR spectroscopy and elemental analysis. The reaction of the resulting compound with the dimeric, complex [η5-CpMo(CO)3#x005D;2 inm-xylene upon refluxing gave the heterometallic cluster Fe2Mo2(μ3-Se)(μ3-AsMe)(μ3-Co)(μ-Co)(Co)5(η5-Cp)2, whose structure was established by X-ray diffraction analysis.

Nature of Bonding in Donor–Acceptor Interactions Exemplified by Complexes of N‐Heterocyclic Carbenes with 1,2,5‐Telluradiazoles

Comprehensive structural, spectroscopic, and quantum chemical analyses of new donor-acceptor complexes between N-heterocyclic carbenes and 1,2,5-telluradiazoles and a comparison with previously known complexes involving tellurenyl cations showed that the dative C-Te bonds cannot be solitarily described with only one Lewis formula. Canonical Lewis formulas that denote covalency and arrows emphasizing ionicity complement each other in varying extents. Evaluation of the relative weights of these resonance forms requires proper bonding description with a well-balanced toolbox of analytical methods. If for conciseness only, one resonance form is used, it must be the most significant one according to the analytical evaluation. If unclear, all significant resonance forms should be displayed.

Ribbed-monofunctionalized iron(II) clathrochelate with tert-butyl sulfide substituents: Synthesis, structure, and thermochemical transformations

A ribbed-monofunctionalized macrobicyclic iron(II) complex with tert-butyl sulfide substituents has been prepared via nucleophilic substitution of its dichloroclathrochelate precursor with tert-butylthiolate ion. This new complex has been characterized using elemental analysis, IR and multinuclear NMR spectroscopy, and the single crystal X-ray diffraction. Its thermal destruction occurs with release of isobutylene and polyunsaturated hydrocarbons giving iron borate, iron fluoropolyborate, and iron nitride as follows from combined thermal analysis and X-ray powder diffraction data.

The first seven-electron triangular tungsten sulfide cluster

A new cluster complex [W3S4(Dppe)3Br3] · 3THF (Dppe = Ph2PCH2CH2PPh2), the first example of a triangular tungsten cluster with a seven-electron core, was synthesized. The molecular and crystal structures of the compound were determined by X-ray diffraction.

Aromatic substitution and dealkylation by alkanetellurolate anions

Abstract Under the action of alkanetellurolate anion phenyl halides undergo aromatic substitution followed by dealkylation of the alkyl phenyl telluride thus formed. The generated benzenetellurolate anion can be either alkylated or oxidized to diphenyl ditelluride, or added to acetylene. Butyl methyl telluride and selenide are demethylated by methanechalcogenolate anions.

Crystal structure of the seven-electron molybdenum cluster [Mo3S4(dppe)3Cl3]∙3.5C4H8O2∙0.5Et2O

The seven-electron neutral cluster complex [Mo3S4(dppe)3Cl3] (dppe = Ph2PCH2CH2PPh2) is obtained by the reduction of the [Mo3S4(dppe)3Cl3]Cl cluster with gallium metal. The molecular and crystal structure of [Mo3S4(dppe)3Cl3]∙3.5C4H8O2∙0.5Et2O solvate is determined by single crystal XRD. The crystallographic data are as follows: monoclinic crystal symmetry, space group C2/c, a = 41.1775(16) Å, b = 17.7178(7) Å, c = 28.9609(9) Å, β = 110.363(1)°, V = 19808.7(13) Å3, Z = 8, dcalc = 1.384 g/cm3.

Paramagnetic triangular rhenium sulfide cluster [Re3S4(Dppe)3(NCS)3]Br

A new cluster [Re3S4(Dppe)3(NCS)3]Br (Dppe = Ph2PCH2CH2PPh2) is synthesized. The molecular and crystal structures of the cluster are determined by X-ray diffraction analysis. The magnetochemical data indicate the high-spin ground state (S = 3/2) of the cluster at room temperature.

A new approach to the synthesis of gallium(III) complexes with α-diimine ligands in the radical anion form

A convenient method for the synthesis of gallium(III) complexes with α-diimine ligands DABMe,Mes (N,N′-(butane-2,3-diylidene)bis(2,4,6-trimethylaniline)) or BIANDipp (1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) in the radical anion form is found. The method includes the reaction of complexes [Co(DABMe,Mes)Cl2] and [Co(BIANDipp)Cl2] with gallium resulting in the transmetallation and one-electron reduction of the ligand. The synthesized complexes [Ga(DABMe,Mes)Cl2] and [Ga(BIANDipp)Cl2] are characterized by X-ray diffraction analysis and EPR spectroscopy.

Syntheses and structures of the cobalt, nickel, and zinc complexes with 1,4-diaza-1,3-butadiene ligands

Several cobalt(II), nickel(II), and zinc(II) complexes with a series of ligands of the 1,4-diaza-1,3-butadiene type bearing aryl (2,6-di-iso-propylphenyl, mesityl) and alkyl (tert-butyl, iso-propyl) substituents at the nitrogen atoms are synthesized. The obtained complexes are characterized by X-ray structure analysis, IR spectroscopy, and elemental analysis.