A radical mechanism of the reaction of molybdenum carbonyl complexes with bis(triethylgermyl)mercury

The reaction of [Cp(CO)₃Mo]₂ with (Et₃Ge)₂Hg occurs in toluene and THF by a radical mechanism. The interaction between [Cp(CO)₃Mo]₂Hg and (Et₃Ge)₂Hg has a radical character only in THF. The formation of Cp(CO)₃MoH at the first stage of these reactions substantially affects the further course of the process.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1648–1650, September, 1993.     

Reactions of 1-(3"-Amino)- and 1-(3"-Acetamido)propylsilatranes with Cobalt(II) Chloride and Dicobalt Octacarbonyl

1-(3"-Amino)propylsilatrane (I) and 1-(3"-acetamido)propylsilatrane (II) react with anhydrous cobalt(II) chloride to give dichlorobis[1-(3"-amino)propylsilatrane]cobalt(II) {Co[NH₂CH₂CH₂CH₂Si(OCH₂CH₂)₃N]₂Cl₂} (III) and dichlorobis[1-(3"-acetamido)propylsilatrane]cobalt(II) {Co[CH₃C(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]₂Cl₂} (IV). Being unstable, compound IV transforms into an imidic acid derivative. Reactions of silatranes I and II with dicobalt octacarbonyl afford hexakis[1-(3"-aminoamido)propylsilatrane]cobalt(II) bis(tetracarbonylcobaltate) {Co[NH₂CH₂CH₂CH₂Si(OCH₂CH₂)₃N]_4.8[HC(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]_1.2}[Co(CO)₄]₂ (V) and hexakis[1-(3"-acetamido)propylsilatrane]cobalt(II) bis(tetracarbonylcobaltate) {Co[CH₃C(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]₆}[Co(CO)₄]₂ (VI), respectively. In acetonitrile, tetracarbonylcobaltate anions of compound VI are oxidized with atmospheric oxygen and moisture to cobalt hydroxocarbonate, giving a carbonate gel (VII).     

Spectroscopic study of compounds possessing a bond of an element of group IVB with hydrogen

Conclusions The frequencies of the valence vibrations of the Si-H bond in trisubstituted silanes depends not only on the inductive effect of substituents, but also on the effects of d-p interaction, ,- and p,-conjugation. An analysis was made of the relative contributions of these effects, depending on the nature of the substituent.For the preceding communications, see [1, 2].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 544–550, March, 1971.     

Synthesis and structure of 1,1′-bis(pentafluorophenyl)tetrahydrodigermane

Dehydrogenation of pentafluorophenylgermane in the presence of catalytic amounts of a Wilkinson complex, certain Rh^I ortho-benzosemiquinolate complexes, or (Ph₃P)₄Pt leads to tetrahydrodigermane, C₆F₅H₂GeGeH₂C₆F₅. X-ray analysis has confirmed thetrans-arrangement of the C₆F₅-cycles at the Ge atoms. The Ge-Ge bond length is 2.394(1) Å. The doublet pattern of the band due to the Ge-H bonds (v 2090 and 2104 cm^–1) in the IR spectrum is probably associated with nonequivalence of the hydrogen atoms in the molecule.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 315–318, February, 1994.     

Synthesis and crystal structure of triphenyl[tris(tetrahydrofuran)]ytterbium, Ph3Yb(THF)3

Triphenyl[tris(tetrahydrofuran)]ytterbium, Ph₃Yb(THF)₃ (1), was synthesized in high yields by the reaction of Yb with an excess of Ph₂Hg or Ph₃Bi in the presence of catalytic amounts of YbI₂(THF)₄ as well as by the reaction of Ph₂Yb(THF)₂ (2) with Ph₂Hg or Ph₃Bi. The crystal structure of complex1 was studied by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 163–166, January, 1998.     

Synthesis of heterobimetallic zinc complexes and their catalytic properties in reactions of CO<Subscript>2</Subscript> with cyclohexene oxide

The reaction of Et₂Zn with NaOCH₂CH₂OH yielded a bimetallic zinc complex NaOCH₂CH₂OZnEt. Its reactions with Ph₃SnCl, Cp₂TiCl₂, and Cp₂LuCl(THF) afforded the corresponding complexes Ph₃SnOCH₂CH₂OZnEt, Cp₂Ti(OCH₂CH₂OZnEt)₂, and Cp₂LuOCH₂CH₂OZnEt. Cp₂Ti(OCH₂CH₂OZnEt)₂ catalyzes copolymerization of CO₂ with cyclohexene oxide at room temperature and atmospheric pressure; the yield of the polycarbonate is 4 g g^–1 catalyst. Ph₃SnOCH₂CH₂OZnEt is catalytically inert under these conditions, and with Cp₂LuOCH₂CH₂OZnEt only the polyether is formed.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1292–1294.Original Russian Text Copyright © 2004 by Nikitinskii, L. Bochkarev, Voronin, Khorshev, Kurskii, M. Bochkarev.This revised version was published online in April 2005 with a corrected cover date.     

Mechanism of Dimerization-Rearrangement of Organosilicon Aroxyls

Organosilicon aroxyls form disiloxybiaryls via C-C dimerization with simultaneous (or subsequent) isomerization of the dimeric intermediate, involving migration of the ortho-organosilyl substituents from carbon to oxygen.     

Polymerization of Ferrocene in an Electrodeless High-Frequency Discharge Helium Plasma: II.1 Structure and Crystallization Dynamics of Plasmochemically Polymerized Films

The main frequencies in the IR spectra of ferrocene and plasmochemically polymerized ferrocene films obtained in the plasma of an electrodeless high-frequency discharge in mixtures of helium and ferrocene are the same. The appearance in the IR spectra of the films of weak bands is associated with partial decomposition of ferrocene molecules in the high-frequency discharge plasma.