The Frustrated Lewis Pairs (FLP) concept recently demonstrated to be a powerful way to activate small molecules and promote a plethora of organic reactions without the help of transition metal-based catalysts. This strategy is based on simple combinations of Lewis acids and bases that are sterically or electronically hindered from forming classical Lewis acid-base adducts. Generally, the Lewis acid is a fluorinated compound of boron or aluminum, and the Lewis base is based in most cases on phosphorous, nitrogen or, seldom, oxygen. To the best of our knowledge, no attempt has been made to isolate, characterize and test in catalysis selenium-based FLPs. In the present contribution, the interaction between sterically encumbered organoselenium compounds, as selenides and selones, and standard Lewis acids, as B(C 6 F 5 ) 3 and less-fluorinated boranes, will be studied by Energy Decomposition Analysis and compared to the interaction of known P-based FLPs. The results indicate that selenium-based FLPs are theoretically possible. For the most promising candidates, the products of the activation of small molecules (H 2 or CO 2 ) will be theoretically studied, to check if the reaction would be thermodynamically favored.
Theoretical Investigation on Selenium-Based Frustrated Lewis Pairs
Ciancaleoni, Gianluca
2020-01-01
Abstract
The Frustrated Lewis Pairs (FLP) concept recently demonstrated to be a powerful way to activate small molecules and promote a plethora of organic reactions without the help of transition metal-based catalysts. This strategy is based on simple combinations of Lewis acids and bases that are sterically or electronically hindered from forming classical Lewis acid-base adducts. Generally, the Lewis acid is a fluorinated compound of boron or aluminum, and the Lewis base is based in most cases on phosphorous, nitrogen or, seldom, oxygen. To the best of our knowledge, no attempt has been made to isolate, characterize and test in catalysis selenium-based FLPs. In the present contribution, the interaction between sterically encumbered organoselenium compounds, as selenides and selones, and standard Lewis acids, as B(C 6 F 5 ) 3 and less-fluorinated boranes, will be studied by Energy Decomposition Analysis and compared to the interaction of known P-based FLPs. The results indicate that selenium-based FLPs are theoretically possible. For the most promising candidates, the products of the activation of small molecules (H 2 or CO 2 ) will be theoretically studied, to check if the reaction would be thermodynamically favored.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
