New cage-like metallasiloxane containing Fe<Superscript>III</Superscript> ions in different coordination spheres

The first cage-like ferrophenyl siloxane containing Fe^III ions in different coordination spheres (four iron ions have a trigonal-bipyramidal coordination and two iron ions have a distorted octahedral coordination) was synthesized by the exchange reaction of sodium phenylsilanolate with Fe^III chloride. An exotic lantern-like structure is formed with the involvement of two metal oxide fragments Fe—O—Fe. The structure of this compound was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 522–524, March, 2007.     

Synthesis and study of the structure of cage-like metallosiloxanes with pair combinations of 3d transition and alkaline earth metals

The selective replacement of Na ions in cage-like (Cu,Na) organosiloxanes in reactions with divalent metal halides was studied. The sandwich-like isomer [PhSiO₂]₆Cu₄Na₄[PhSiO₂]₆ forms the corresponding bimetallic complexes [PhSiO₂]₆Cu₄M₂[PhSiO₂]₆ (M = Cu, Zn, Mg, Sr, Ba) retaining a sandwich-like structure (in 60–90% yields) regardless of the metal ion size in MCl₂. Under similar conditions, the reactions of the globular isomers [RSiO₂]₁₂Cu₄Na₄ (R = Ph, Me, Vin) with CuX₂ (X = Cl or Br) afforded insoluble polymer products. The reaction in dioxane or THF in the presence of DMSO gave the crystalline globular-type metal complexes [RSiO₂]₁₂Cu₄[CuX]₄, in which Na ions are replaced by CuX groups. The compositions and structures of the synthesized metal complexes were studied by X-ray diffraction, elemental analysis, and destructive silylation combined with gel permeation chromatography and ¹H NMR spectroscopy.     

Polymerization of hexaethylcyclotrisiloxane during the synthesis of carbofunctional oligo(diethylsiloxane diols)

Oligo(diethylsiloxane diols) carrying β-oxyethoxymethyl terminal groups are synthesized for the first time by the cationic polymerization of hexaethylcyclotrisiloxane in the presence of bis(β-oxyethoxymethyl)tetramethyldisiloxane with the use of sulfuric acid or the cationite KU-23 as a catalyst. It is shown that, along with oligo(diethylsiloxane diols), the products of rearrangement of diethylsiloxane chains, such as octaethylcyclotetrasiloxane and higher cycles, are formed. The reaction of dipotassium salts of oligo(diethylsiloxane diols) with chlorosilanes of the formula ClSi(CH₃)₂CH₂O(CH₂)₂OCOCH₃ yields acetoxy-terminated oligomers that contain octaethylcyclotetrasiloxane and higher cycles as well.     

Studying the structure of siloxane-urethane-ethylene oxide block copolymers

The structure of siloxane-urethane-ethylene oxide block copolymers is studied by means of atom force microscopy (AFM) and scanning electron microscopy (SEM). The degree of copolymer crystallinity is determined by X-ray diffraction. A correlation between the obtained results is established.     

Studying the structure of polysiloxane carbonate urethanes

The structure of amorphous polysiloxane carbonate urethanes is studied by AFM, SEM, and TEM. It is found that the polymer structure depends on the nature of solvent used for film casting.