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 |
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Authors: | Yu E Ovchinnikov S A Pogozhikh I V Razumovskaya A G Shipov E P Kramarova S Yu Bylikin Vad V Negrebetsky Yu I Baukov |
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Institution: | (1) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813 Moscow, Russian Federation;(2) V. I. Lenin Moscow State Pedagogical University, 1 ul. M. Pirogovskaya, 119891 Moscow, Russian Federation;(3) Russian State Medical University, 1 ul. Ostrovityanova, 117869 Moscow, Russian Federation |
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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.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 997–1007, May, 1998 |
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Keywords: | silicenium ions five-coordinate silicon cation-anionic complexes X-ray diffraction analysis quantum-chemical calculations MNDO/PM3 method |
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