Abstract
The reactions of bis(chloromethyl)dichlorosilane withN-trimethylsilyl lactams andN-trimethylsilyl-N-methylacetamide taken in a ratio of 1∶2 followed either by treatment with HgCl2 in the presence of atmospheric moisture or by hydrolysis under a wet atmosphere afforded cation-anionic complexes, which contain disiloxane dications of the general formula [L2SiOSiL2]2+ (L is the lactamomethyl orN-methylacetamidomethyl bidentate ligand) and hexachlorodimercurate, tetrachloromercurate, and hydroxonium trichloride counter-ions, respectively. X-ray diffraction analysis demonstrated that the disiloxane dications in these complexes contain two five-coordinate Si atoms and occur as silicenium ions stabilized through two O→Si coordination bonds. In the case of lactamomethyl ligands, the disiloxane dications exist as diastereomers whose bischelate ligands adopt opposite configurations, whereas whenN-methylacetamidomethyl ligands are present, the bischelate ligands adopt identical configurations. The first example of the presence of a hydroxonium trichloride ion as a counter-ion in the crystal has been found. It consists of the hydroxonium cation, which holds three Cl− anions through strong hydrogen bonds.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 997–1007, May, 1998
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Ovchinnikov, Y.E., Pogozhikh, S.A., Razumovskaya, I.V. et al. Synthesis and crystal and molecular structures of cation-anionic complexes of five-coordinate silicon-containing disiloxane dications with lactamomethyl andN-methylacetamidomethyl C,O-chelating ligands. Russ Chem Bull 47, 967–978 (1998). https://doi.org/10.1007/BF02498170
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DOI: https://doi.org/10.1007/BF02498170