The Role of Ate Complexes in the Lithium‐Sulfur,Lithium‐Selenium and Lithium‐Tellurium Exchange Reactions |
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Authors: | HansJ Reich Birgir
Gudmundsson DPatrick Green MartinJ Bevan IevaL Reich |
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Abstract: | Hypervalent ate complexes are presumptive intermediates in the metal‐halogen, metal‐tellurium, and related exchange reactions. The effect of o,o′‐biphenyldiyl vs. diphenyl substitution on formation of tellurium ate complexes was studied by a kinetic technique and by NMR spectroscopy. Only a modest increase in the association constant (Kate) was measured. When Li/M exchanges of o,o′‐biphenyldiyl sulfides and selenides were made intramolecular by means of a m‐terphenyl framework ( 12‐S, 12‐Se, 21 ), enormous increases (>109) in the rate of Li/S and Li/Se exchange were observed compared to acyclic models. Apparently, these systems are ideally preorganized to favor the T‐shaped geometry of the hypervalent intermediates. For the selenium systems, ate complex intermediates ( 20‐Se, 26 ) were detected spectroscopically in THF‐ or THF/HMPA‐containing solutions. A DNMR study showed that Li/Se exchange was substantially faster than exchange of the lithium reagents with the ate complex. Therefore, these ate complexes are not on the actual Li/Se exchange pathway. |
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