Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

Compounds based on new cyanide cluster anions [{Mo₆I₈}(CN)₆]^2–, trans-[{Mo₆I₈}(CN)₄(MeO)₂]^2– and trans-[{W₆I₈}(CN)₂(MeO)₄]²⁻ were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo₆I₈}⁴⁺ and {W₆I₈}⁴⁺ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo₆I₈} and {W₆I₈} cluster cores can be achieved by coordination of cyanide ligands.     

Synthesis of benzo-1,3-ditellurole and its precursors

Poly(o-phenyleneditelluride) 6 has been prepared by the reduction of 1,2-bis(trichlorotelluro)benzene obtained by treatment of 1,2-bis(trimethylsilyl)benzene with TeCl₂. The reduction of 6 with NaBH₄ in ethanol solution affords sodium benzene-1,2-ditellurolate, which, upon treatment with methylene bromide, forms benzo-1,3-ditellurole in 40–47% yield. Benzo-1, 3-ditellurole has also been synthesized in 18–20% yeild by the reaction of 1,2-bis(trimethylslyl)benzene with bis(trichlorotelluro)methane, with subsequent reduction of the product, 1,1,3,3-tetrachlorobenzo-1,3-ditellurole.     

Telluraxanthene

Telluraxanthene was obtained by intramolecular electrophilic cyclization of 2-trichlorotelluriodiphenylmethane with subsequent reduction of the intermediately formed 10,10-dichlorotelluraxanthene. The chemical reactions that occur at the tellurium atom and the methylene group of telluraxanthene were studied. The lower limit of the activation energy of pyramidal inversion at the onium tellurium atom in telluroniaxanthenyldimedone ylid was determined by PMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1342–1349, October, 1980.     

Synthesis of 2-substituted benzo-1,3-ditelluroles

A method for the synthesis of 2-phenylbenzo-1,3-ditellurole by the reaction of disodiumo-benzeneditellurolate with benzylidene chloride was proposed. 2-Methylbenzo-1,3-ditellurole and benzo-1,3-ditellurole-2-carboxylic acid were prepared by the reaction of 2-lithiobenzo-1,3-ditellurole with MeI and CO₂, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1132–1134, June, 2000.     

Comparative dissociation of peptide polyanions by electron impact and photo-induced electron detachment

We compare product-ion mass spectra produced by electron detachment dissociation (EDD) and electron photodetachment dissociation (EPD) of multi-deprotonated peptides on a Fourier transform and a linear ion trap mass spectrometer, respectively. Both methods, EDD and EPD, involve the electron emission-induced formation of a radical oxidized species from a multi-deprotonated precursor peptide. Product-ion mass spectra display mainly fragment ions resulting from backbone cleavages of C_α-C bond ruptures yielding a and x ions. Fragment ions originating from N-C_α backbone bond cleavages are also observed, in particular by EPD. Although EDD and EPD methods involve the generation of a charge-reduced radical anion intermediate by electron emission, the product ion abundance distributions are drastically different. Both processes seem to be triggered by the location and the recombination of radicals (both neutral and cation radicals). Therefore, EPD product ions are predominantly formed near tryptophan and histidine residues, whereas in EDD the negative charge solvation sites on the backbone seem to be the most favorable for the nearby bond dissociation.     

Insights into the mechanism of O₂ formation and release from the Mn₄O₄L₆ "cubane" cluster

To probe photoinduced water oxidation catalyzed by the Mn?O?L? cubane clusters, we have computationally studied the mechanism and controlling factors of the O? formation from the [Mn?O?L?] catalyst, 6. It was demonstrated that dissociation of an L = H?PO?? ligand from 6 facilitates the direct O-O bond formation that proceeds with a 28.3 (33.4) kcal/mol rate-determining energy barrier at the transition state TS1. This step (the O-O single bond formation) of the reaction is a two-electron oxidation/reduction process, during which two oxo ligands are transformed into to μ2:η2-O?2? unit, and two ("distal") Mn centers are reduced from the 4+ to the 3+ oxidation state. Next two-electron oxidation/reduction occurs by "dancing" of the resulted O?2? fragment between the Mn1 and Mn2/Mn(2')-centers, keeping its strong coordination to the Mn(1')-center. As a result of this four-electron oxidation/reduction process Mn centers of the Mn?-core of I transform from {Mn1(III)-Mn(1')(III)-Mn2(IV)-Mn(2')(IV)} to {Mn1(II)-Mn(1')(II)-Mn2(III)-Mn(2')(III)} in IV. In other words, upon O? formation in cationic complex [Mn?O?L?](+), I, all four Mn-centers are reduced by one electron each. The overall reaction I → TS1 → II → III → TS2 → IV → TS3 → V → VI + O? is found to be exothermic by 15.4 (10.5) kcal/mol. We analyze the lowest spin states and geometries of all reactants, intermediates, transition states, and products of the targeted reaction.