Addition of 1,1,1,3-tetrachloropropane to 1-hexene,initiated by system Fe(CO)5+HMPA+p-ClC6H4SO2NCl2

Conclusions The addition of N,N-dichloro-p-chlorobenzenesulfonamide to the initiating system Fe-(CO)₅+HMPA increases the yield of 1,3,3,5-tetrachlorononane in the reaction of 1,1,1,3-tetrachloropropane with 1-hexene and lowers the reaction temperature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2618–2620, November, 1979.     

Chemical transformations of 1,3,3,5-tetrachlorononane initiated by Fe(CO)5, Me(CO)6 and Mn2(CO)10 systems

Conclusions A study was carried out on the competitive reactions of CICH₂CH₂ClCH₂CHClC₄H₉ (A) generated from 1,3,3,5-tetrachlorononane by the action of Fe(CO)₅, Mo(CO)₆, and Mn₂(CO)₁₀ systems. The Mn₂(CO)₁₀ systems were most efficient for obtaining the reaction of (A) radicals with hydrogen donors, while the Fe(CO)₅ systems were most efficient for obtaining rearrangements of (A) radicals with 1,5- and 1,6-hydrogen migration and subsequent reaction with a chlorine donor and Mo(CO)₆ and Mn₂(CO)₁₀ systems were most efficient in effecting disproportionation of (A) radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2623–2626, November, 1984.     

Reaction of bromoform and iodoform with acrylic monomers initiated by Fe(CO)5+DMF

Conclusions The Fe(CO)₅ + DMF system, in contrast to peroxide initiation, permits us to carry out the addition of bromoform with selective cleavage of the C-Br bond to readily polymerizing acrylonitrile, methyl acrylate, and methyl methacrylate. Iodoform was shown to be significantly more active than bromoform in these reactions, which permits carrying out the radical addition and telomerization of iodoform in bromoform at lower temperature than without solvent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1904–1906, August, 1987.     

Fluxional behavior of (CO)4Fe(u-AsMe2)Mo(CO)2(C5H5)

The ¹H and ¹³C NMR spectra of the heterobimetallic compound (CO)₄Fe(μ-AsMe₂)Mo(CO)₂(C₅H₅) reveal three different fluxional processes.     

The oxidation of Co2(CO)8, Mn2(CO)10 and Fe(CO)5 by dibenzoyl peroxide. Kinetics and mechanism

Summary Dicobalt octacarbonyl in toluene solution can be quantitatively oxidized at room temperature with dibenzoyl peroxide to cobalt(II) benzoate and carbon monoxide. The rate of CO evolution is first order in dicobalt octacarbonyl, first order in dibenzoyl peroxide, and negative first order in CO. Similar behaviour leading to manganese(II) benzoate is observed with dimanganese decacarbonyl. Sixteen electron rather than seventeen electron intermediates are involved in these reactions. In contrast to the dinuclear carbonyls, Fe(CO)₅ is oxidized by dibenzoyl peroxide in an autocatalytic reaction.     

Reaction of 1,1,1-trichloroethane or carbon tetrachloride with allyl chloride,initiated by the Fe(CO)5-isopropanol system

Conclusions The reaction of CCl₃CH₃ and CCl₄ with allyl chloride in the presence of Fe(CO)₅ and isopropanol yields a mixture of products, the main component of which is the adduct RCCl₂CH₂CHClCH₂Cl (R=Cl, CH₃). The RCCl₂CH₂CH= CH₂ were also isolated, which represent the fragmentation product of the intermediately formed radical and its adduct with the telogen, namely RCCl₂CH₂CHClCH₂CCl₂R.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2004–2008, September, 1973.     

Thermal homolytic fission of the MoMo bond in (h5 -C5H5)2Mo2(CO)6

Kinetic studies of reactions of the MoMo bonded complex (h⁵-C₅H₅)₂Mo₂(CO)₆ in decalin show that it undergoes reversible homolytic fission and that the activation enthalpy required to break the MoMo bond is 135.9 ± 2.2 kJ mol^?1.     

Hydrogenolysis of the C-Cl bond of the dichloromethylene group in polychloroalkanes initiated by Fe(CO)5, Mn2(CO)10, or tert-butyl peroxide in combination with triethylsilase

Conclusions The dichloromethylene group in polychloroalkanes is selectively reduced by the action of Fe(CO)₅, Mn₂(CO)₁₀ or (Me₃CO)₂O in combination with Et₃SiH to a chloromethylene group. The Mn₂(CO)₁₀-Et₃SiH system is the most efficient in this reaction.Translated from Izvestiya Akademii Nauk SSSK, Seriya Khimicheskaya, No. 5, pp. 1136–1138, May, 1986.     

Ge4Br4[Mn(CO)5]4 and Ge6Br2[Mn(CO)5]6: first germanium cluster compounds containing Mn(CO)5 ligands

Cluster compounds of germanium exhibiting germanium-germanium bonds, where the germanium atoms are additionally bound to transition metal ligands, are rare. Here a synthetic pathway to such cluster compounds is described, starting from metastable Ge I halide solutions leading to the two cluster compounds Ge4Br4[Mn(CO)5]4 and Ge6Br2[Mn(CO)5]6, being the first examples of germanium cluster compounds bearing Mn(CO)5 ligands. The Ge6 compound exhibits a novel arrangement of germanium atoms that has not been previously observed in ligand stabilized cluster compounds of germanium, neither with organic nor with transition metal ligands. The bonding situation inside the cluster compounds is discussed, together with a possible reaction pathway that opens the way to metalloid cluster compounds of germanium exhibiting Mn(CO)5 ligands.     

Reaction of α,α,ω-trichloroalkenes with 1,1,1-trichloroethane and 1,1,1,3-tetrachloropropane,accompanied by rearrangement of radicals

Conclusions In the reaction of CCl₃CH₃ with CCl₂=CHCH₂CH₂CH₂Cl, and of CCl₃CH₂CH₂Cl with CCl₂= CHCH₂Cl, initiated by Fe(CO)₅+DMF, the main addition products are respectively compounds of structure HCCl₂CH(CCl₂CH₃)CH₂CH₂CHCl₂ and HCCl₂CH(CCl₂CH₂CHCl₂)CH₂C1. The formation of these compounds was explained by the isomeriza'tion of the radical-adducts CCl₂CH(CCl₂CH₃)CH₂CH₂CH₂Cl and CCl₂CH(CCl₂CH₂CH₂Cl)CH₂Cl, with migration of a hydrogen atom from the CH₂Cl groups found in the 5 position to the radical center.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1857–1861, August, 1980.     

Reaction of 2-amino-5-h alop yridines with methyl acrylate

Two isomeric bicyclic dihydropyridopyrimidinones (II and IV), the methyl esters of the corresponding N-pyridyl--alanines (V), and a number of other compounds are formed during the reaction of methyl acrylate with 2-amino-5-halopyridines in the presence of acid catalysts. Compounds II and IV were hydrolytically cleaved, and some derivatives of N-(5-halo-2-pyridyl)--alanines were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 215–219, February, 1971.     

Complexes in polymers II: FT-IR spectra,iodine oxidation,and photochemistry of [(η5-C5H)Fe(CO)2]2, [(η5-C5H5)Mo(CO)3]2 and Mn2(CO)10 in polystyrene,poly(methyl methacrylate) and polystyrene–polyacrylonitrile copolymer

The infrared spectra of [CpFe(CO)₂]₂, [CpMo(CO)₃]₂ and Mn₂(CO)₁₀ (Cp=η-C₅H₅) embedded in films of polystyrene (PS), poly(methyl methacrylate) (PMMA), and polystyrene-polyacrylonitrile (PS? AN), are comparable with those of the dimers in toluene, ethyl acetate and acetonitrile, respectively. Irradiation of the embedded dimers with UV light led to decomposition in PS and PMMA, while in PS? AN the complexes Cp₂Fe₂(CO)₃PS? AN and Mn₂(CO)₉PS? AN were formed, wherein a pendant nitrile group is coordinated to one of the metal atoms. Exposure of the embedded dimers to iodine vapour gave CpFe(CO)₂I, CpMo(CO)₃I and Mn(CO)₅I with the reaction being much slower in PMMA than in PS.