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Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation
The crystal structures of (H(3)C)(2)O, H(2)SiCl(2) and an adduct of these were determined by low-temperature X-ray crystallography on crystals grown in situ at low temperatures on a diffractometer. The adduct of (H(3)C)(2)O and H(2)SiCl(2) has the composition [(H(3)C)(2)O.H(2)SiCl(2)](2) and contain...
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Published in: | Dalton transactions : an international journal of inorganic chemistry 2004-08 (16), p.2578-2581 |
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Main Authors: | , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | The crystal structures of (H(3)C)(2)O, H(2)SiCl(2) and an adduct of these were determined by low-temperature X-ray crystallography on crystals grown in situ at low temperatures on a diffractometer. The adduct of (H(3)C)(2)O and H(2)SiCl(2) has the composition [(H(3)C)(2)O.H(2)SiCl(2)](2) and contains a four-membered Si(2)O(2) ring, with the Cl atoms pointing to the outside and the Si-H functions pointing to the inner side of the ring. The Si(2)O(2) ring has two longer and two shorter SiO bonds and thus deviates from a square. Quantum chemical calculations give a geometry for [(H(3)C)(2)O.H(2)SiCl(2)](2) which has D(2h) symmetry and allow to obtain an estimate for the adduct formation energies, which are -13.4 kJ mol(-1) for the formation of the mono adduct [(H(3)C)(2)O + H(2)SiCl(2)-->(H(3)C)(2)O.H(2)SiCl(2)], -14.4 kJ mol(-1) for the dimerization of two mono adducts [(H(3)C)(2)O.H(2)SiCl(2)-->[(H(3)C)(2)O.H(2)SiCl(2)](2)] and -41.2 kJ mol(-1) for the reaction 2 (H(3)C)(2)O + 2 H(2)SiCl(2)-->[(H(3)C)(2)O.H(2)SiCl(2)](2). The results are used to rationalize the strongly reduced reactivity of H(2)SiCl(2) towards nucleophilic substitution reactions in (H(3)C)(2)O at low temperatures. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/B405684A |