Reversible Reactions of Ethylene with Distannynes Under Ambient Conditions
Abstract
Ethylene’s cycloadditions to unsaturated hydrocarbons occupy well-established ground in classical organic chemistry. In contrast, its reactivity toward alkene and alkyne analogs of carbon’s heavier-element congeners silicon, germanium, tin, or lead has been little explored. We show here that treatment of the distannynes AriPr4SnSnAriPr4 [AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2, 1] or AriPr8SnSnAriPr8 [AriPr8 = C6H-2,6(C6H2-2,4,6-iPr3)2-3,5-iPr2, 2] with ethylene under ambient conditions affords the cycloadducts ArPir4Sn(μ2:η1:η1-C2H4)2Sn︹ArPir4 (3) or ArPir8Sn(μ2:η1:η1-C2H4)2Sn︹ArPir8 (4) that were structurally and spectroscopically characterized. Ethylene incorporation in 3 and 4 involves tin-carbon σ bonding and is shown to be fully reversible under ambient conditions; hydrocarbon solutions of 3 or 4 revert to the distannynes 1 or 2 with ethylene elimination under reduced pressure or upon standing at ~25°C. Variable-temperature proton nuclear magnetic resonance studies showed that the enthalpies of reaction were near -48 (3) and -27 (4) kilojoules per mole.
- Publication:
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Science
- Pub Date:
- September 2009
- DOI:
- 10.1126/science.1176443
- Bibcode:
- 2009Sci...325.1668P
- Keywords:
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- CHEMISTRY