| Autor: |
A.L. Spek, Rjf Jans, G Vankoten, Kees Vrieze, Rr Andrea, B. Kojic-Prodic, Jl Deboer |
| Rok vydání: |
2010 |
| Předmět: |
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| Zdroj: |
Recueil des Travaux Chimiques des Pays-Bas. 105:317-325 |
| ISSN: |
0165-0513 |
| DOI: |
10.1002/recl.19861050915 |
| Popis: |
Aminosulphines (R1R2N)(R3)CSO coordinate via the oxygen atom to dimethyltin dichloride. This η1-O coordination was established by the X-ray structure of Me2SnCl2[η1-O-(Me(Ph)NC(Ph)SO)] which consists of monomers connected to dimers with unequal Sn-Cl bridges of 2.544(1) and 3.307(1) A. The tin centres have a distorted octahedral arrangement. The Sn-O distance is 2.269(3) A and the Sn-O-S angle is 129.1(2)°. Theoretical calculations showed that the negative charge on the sulphine oxygen atom is enhanced by conjugation of the πCS bond with the amino lone pair of the NR1R2 group. Of the other sulphines tested, only 9-fluorenethione S-oxide was found to coordinate to Me2SnCl2, likewise in the η1-O coordination mode. The η1-O coordination to tin destabilizes the sulphine fragment as was shown by the stoichiometric decomposition of the sulphine into the corresponding ketones and thioketones. A possible route for the decomposition process is proposed involving the formation of an oxathiiran intermediate. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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