ESR study of the reaction of decacarbonyidimanganese with thallium(i) 3,6-di-tert-butyl-o-benzosendquinolate in solutions

The reaction of decacarbonyldimanganese Mu₂(CO)₁₀ (1) With thallium(t) 3,6-di-tert-butyl-o-benzosemiquinolate (2) in solution was studied by ESR spectroscopy. Irradiation of solutions containing1 and2 in organic solvents with visible light at 220–280 K leads totrinuclear MnTlMn complex (3). An analysis of hyperfine structure parameters indicates that3 is a semiquinone complex of thallium. A possible mechanism of the formation of complex3 and its molecular structure was discussed.Translated fromIzveshya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 95–98, January, 1996.     

Sterically Hindered o‐Quinone Annulated with Dithiete: A Molecule Comprising Diolate and Dithiolate Coordination Sites

A new stable sterically hindered o‐quinone annelated with a 1,2‐dithiete ring was prepared by using mild conditions. The skeleton of the compound comprises diolate and dithiolate functions that have the potential to bind metals leading to the corresponding complexes. The reactivity of this compound as a ligand with respect to both coordination sites was studied. Reactions with metals indicate that the o‐quinone function is reduced in the first stage to give semiquinonate and catecholate complexes. The dithiolate coordination site was involved in the reaction in a few cases only after diolate was bound. A trinuclear manganese complex with coordination on both sites was obtained and characterized by EPR spectroscopy. The electrochemical study of this quinone fused with dithiete is reported.     

Coordination radical polymerization of methyl methacrylate,initiated by the azobis(isobutyronitrile)–tri-<Emphasis Type="Italic">n</Emphasis>-butylborane binary system

A procedure for coordination radical polymerization of methyl methacrylate in the bulk, initiated by the azobis(isobutyronitrile)–tri-n-butylborane binary system at 60°С, was developed. Butyl radicals participating in the initiation step were detected by EPR. These radicals are generated by complexation of cyanoisopropyl radicals with trialkylborane. The radical at the boron atom transforms from the C-centered to N-centered structure with the subsequent S_R2 reaction and fast generation of n-butyl radicals. As found by NMR and confirmed by kinetic studies, the tri-n-butylborane–initiator–monomer system stimulates generation of propagating poly(methyl methacrylate) radicals.     

Thermodynamic characteristics of bis(η6-ethylbenzene)chromium fulleride

The temperature dependence of heat capacity of crystalline bis(η⁶-ethylbenzene)chromium fulleride [(η⁶-EtPh)₂Cr]^·+ [C₆₀]^·− was studied in adiabatic vacuum calorimeter in the range of 6.7 to 344 K with an error of ±0.3%. Dependence of the parameters of EPR signal of bis(η⁶-ethylbenzene)chromium fulleride on temperature was studied by electron paramagnetic resonance (EPR) in the range of 120 to 290 K. In the range of 204 to 246 K, upon heating, reversible endothermic transformation was recorded, which is caused by the dissociation of dimer (C₆₀⁻)₂ and formation of fulleride [(η⁶-EtPh)₂Cr]^·+ [C₆₀]^·−; its standard thermodynamic parameters were estimated and analyzed. Standard thermodynamic functions were calculated by the experimental data obtained: heat capacity, enthalpy, entropy, and Gibbs function of fulleride dimmer in the range of T → 0 to 204 K and monomer complex [(η⁶-EtPh)₂Cr]^·+ [C₆₀]^·− in the range of 246 to 344 K. Standard thermodynamic properties of fulleride under study, fullerides studied earlier, and fullerite C₆₀ were compared.     

Preparation of sodium and bisarenechromium fullendes containing esters of ethylene glycol,diethylene glycol,crown ethers,methoxyarenes, and N-ethyl-N-phenylbenzamide

Russian Chemical Bulletin - The sodium and bis(arene)chromium salts of monosubstituted hydrofullerides, containing bis(3,4-dimethoxyphenyl)phenylmethane, 2,6-bis(4-methoxyphenyl)-4-phenylpyridine,...     

The thermodynamic properties of bis(η6-o-xylene)chromium(I) fulleride over the temperature range from T → 0 to 340 K

The temperature dependence of the heat capacity of bis(η⁶-o-xylene)chromium(I) fulleride, [(η⁶-(o-xylene))₂Cr]^+?[C₆₀]^??, over the temperature range 6–340 K was measured on an adiabatic vacuum calorimeter. The low-temperature (20 K ≤ T ≤ 50 K) heat capacity was subjected to multifractal processing; conclusions about the heterodynamic character of the structure were drawn. The experimental data were used to calculate the standard thermodynamic functions C _p ^° (T), H ^°(T)-H ^°(0), S ^°(T), and G ^°(T)-H ^°(0) over the temperature range from T → 0 to 340 K and estimate the standard entropy of fulleride formation from simple substances at 298.15 K. The standard thermodynamic characteristics of [(η⁶-(o-xylene))₂Cr]^+?[C₆₀]^?? were compared with those of the initial fullerene C₆₀.     

Reaction of 3,4,6-Triisopropyl-<Emphasis Type="Italic">о</Emphasis>-benzoquinone with 3,4,6-Triisopropylcatechol

Formation of protonated 3,4,6-triisopropylsemiquinone radicals in solution of a mixture of 3,4,6- triisopropyl-о-benzoquinone and 3,4,6-triisopropylcatechol was shown using ESR spectroscopy. Heating the mixture to 110°С leads to the formation of the condensation products, additional amount of 3,4,6-triisopropylcatechol, and evolution of propylene. Mathematical simulation of the kinetics of the reaction was performed.     

A reaction of 3,6-di(tert-butyl)-4-chloro-1,2-benzoquinone with potassium ethyl xanthate. New sulfur-containing o-quinones

In a reaction of 3,6-di(tert-butyl)-4-chloro-1,2-benzoquinone with potassium ethyl xanthate, the halogen atom was replaced by the ethyl xanthate group. Acid hydrolysis of the product gave 4,7-di(tert-butyl)-5,6-dihydroxy-1,3-benzodithiol-2-one containing a pyrocatechol fragment, which was oxidized into the corresponding quinone. When irradiated in solution with visible light, this quinone quantitatively eliminated a CO molecule with contraction of the ring to a five-membered one. The quinones obtained were studied as ligands in coordination spheres of metals by ESR spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 683–686, April, 2006.     

ESR study of radical anions ando-semiquinone metal complexes—5,5′-di-tert-butyl-2,2′-dimethylbiphenyl-3,4,3′,4′-diquinone derivatives

The influence of the nature of the metal (metallofragment) on the spin density distribution in radical anions ando-semiquinone metal complexes (derivatives of sterically hindered 5,5′-di-tert-butyl-2,2′-dimethylbiphenyl-3,4,3′,4′-diquinone) was studied by ESR spectroscopy. Despite the difference in the characters of the spin density distribution between the radical anion derivatives (M=Li, Na, K, and CoCp₂) ando-semiquinone complexes (ML_n=Tl, SnPh₃, TlMe₂, Cu(PPh₃)₂, Cu(CNR)₂, and Mn(CO)₄) in all cases significant delocalization of the spin density of an unpaired electron into theo-quinone ring is observed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 904–907, May, 1998.