Reaction of chloro- and bromo-alkyl substituted silanes CCl2XCH2CHXSi(CH3)3 with zinc

Conclusions In the reaction of CCl₃CH₂CHClSiMe₃ and CCl₂rCH₂CHBrSiMe₃ with zinc, trimethylsilyl cyclopropanes are formed in addition to other products. Depending on the halogen and the conditions, reductive dimerization and hydrogenolysis also play a marked role. Under selected conditions, a bromine atom in the-position to the SiMe₃ group is more readily reduced than a chlorine atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1613–1616, July, 1987.     

Reduction of (1,3-diformylindenyl)cyclopentadienylruthenium derivatives

The reduction of the (1,3-diformylindenyl)cyclopentadienylruthenium derivatives {η⁵-1,3-(CHO)₂C₉H₅}RuCp (Cp = C₅H₅), {η⁵-1,3-(CHO)₂C₉H₅}RuCp* (Cp* = C₅Me₅), and {η⁵-1,3-(CHO)₂C₉H₅}RuCpF (Cp^F = C₅Me₄CF₃) with NaBH₄ or LiAlH₄ under mild conditions affords the [1,3-bis(hydroxymethyl)indenyl]cyclopentadienylruthenium complexes {η⁵-1,3-(CH₂OH)₂C₉H₅}RuCp, {η⁵-1,3-(CH₂OH)₂C₉H₅}RuCp*, and {η⁵-1,3-(CH₂OH)₂C₉H₅}-RuCp^F, respectively, in good yields.     

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.     

New one-pot methods for the synthesis of metallonium dications [1,2-(η5:σ:σ-C5Me3(CH2)2)(η5-Cp*)Os]2+ and [1,1"-(η5:σ-C5Me4CH2)2Os]2+ based on decamethylosmocene or its derivatives

The reaction of Cp*₂Os or [Cp*₂OsH]⁺PF₆ ^– with oleum on heating or UV photolysis of Cp*₂Os in oleum under an inert atmosphere afforded two metallonium dications, viz., [1,2-(⁵::-C₅Me₃(CH₂)₂)(⁵-Cp*)Os]²⁺ and [1,1"-(⁵:-C₅Me₄CH₂)₂Os]²⁺. The structures of these dications were confirmed by the results of their alkoxylation. The [Os(H)₂(Cp*)₂]²⁺ and [Os(H)(Cp*)(C₅Me₄CH₂)]²⁺ dications were detected as intermediates in the above syntheses. All compounds were characterized by NMR spectroscopy. Calculations of the dications were carried out using the density functional theory (DFT).     

New one-step methods for the synthesis of the metallonium dication [Ru(η5-C5Me5)(η5:σ:σ-C5Me3(CH2)2]2+ and its heteroannular analog starting from decamethylruthenoceneand its heteroannular analog starting from decamethylruthenocene

The reaction of decamethylruthenocene with oleum or with an oleum—acid (CF₃SO₃H or CF₃CO₂H) mixture as well as UV photolysis of a Cp^* ₂Ru solution in CF₃SO₃H in the presence of a small amount of oleum afforded two metallonium dications,viz., [Ru(η⁵-C₅Me₅)(η⁵:σ:σ-C₅Me₃(CH₂)₂]²⁺ and [Ru(H₂)(η⁵:σ:-C₅Me₄CH₂)₂]²⁺. The structures of these dications were confirmed by the results of their alkaline hydrolysis and NMR spectra. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 517–522, March, 2000.