P and N based o-phenylene Frustrated Lewis Pairs: A theoretical and experimental study

The last decade has experienced a remarkable renaissance in main group chemistry particularly with the discovery in 2006 that frustrated Lewis pairs (FLPs) can heterolytically split dihydrogen.[1] Since then, an increasing... [ view full abstract ]

The last decade has experienced a remarkable renaissance in main group chemistry particularly with the discovery in 2006 that frustrated Lewis pairs (FLPs) can heterolytically split dihydrogen.^[1] Since then, an increasing interest was dedicated to the reactivity of FLP’s and they have been reported to activate a variety of small molecules and can be used as organocatalysts in hydrogenation reactions. The unusual reactivity of FLP is due to the intermolecular or intramolecular combination of unquenched Lewis acid and base moieties. Consequently, a plethora of such systems has since been expanded to include a wide range of donors and acceptors.^[2] Recently, an ansa-aminoborane was reported as a catalyst for hydrogenation of unactivated multiple CC bonds.^[3] 

In this poster presentation, a comparison between P and N based frustrated Lewis pairs containing an o-phenylene backbone will be discussed. Their reactivity towards H₂, followed by protonative cleavage of the aryl ring and further reactivity with small molecules will be reported using a combined experimental and theoretical approach.

[1] Welch, G.C., San Juan, R.R., Masuda, J.D. and Stephan, D.W., Science, 314 (2006) 1124.
[2] Bontemps, S., Bouhadir, G., Miqueu, K., Bourissou, D., J. Am. Chem. Soc., 128 (2006), 12056.
[3] Chernichenko, K., Madarasz, A., Papai, I., Nieger, M., Leskela, M., Repo, T., Nature chem, 5 (2013), 718.