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Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners
Author(s) -
Molitor Sebastian,
Gessner Viktoria H.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201601356
Subject(s) - chemistry , alkali metal , reactivity (psychology) , lithium (medication) , reagent , ether , carbene , inorganic chemistry , crown ether , selectivity , metal , potassium , medicinal chemistry , organic chemistry , ion , catalysis , medicine , alternative medicine , pathology , endocrinology
As a result of the increased polarity of the metal–carbon bond when going down the group of the periodic table, the heavier alkali metal organyl compounds are generally more reactive and less stable than their lithium congeners. We now report a reverse trend for alkali metal carbenoids. Simple substitution of lithium by the heavier metals (Na, K) results in a significant stabilization of these usually highly reactive compounds. This allows their isolation and handling at room temperature and the first structure elucidation of sodium and potassium carbenoids. The control of stability was used to control reactivity and selectivity. Hence, the Na and K carbenoids act as selective carbene‐transfer reagents, whereas the more labile lithium systems give rise to product mixtures. Additional fine tuning of the M−C interaction by means of crown ether addition further allows for control of the stability and reactivity.