title: Facile splitting of hydrogen and ammonia by nucleophilic activation at a single carbon center.
abstract: In possessing a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble transition metal centers and thus could potentially mimic their chemical behavior. Although singlet di(amino)carbenes are inert toward dihydrogen, it is shown that more nucleophilic and electrophilic (alkyl)(amino)carbenes can activate H2 under mild conditions, a reaction that has long been known for transition metals. However, in contrast to transition metals that act as electrophiles toward dihydrogen, these carbenes primarily behave as nucleophiles, creating a hydride-like hydrogen, which then attacks the positively polarized carbon center. This nucleophilic behavior allows these carbenes to activate NH3 as well, a difficult task for transition metals because of the formation of Lewis acid-base adducts.
authors: UCR-CNRS Joint Research Chemistry Laboratory (UMI 2957), Department of Chemistry, University of California, Riverside, CA 92521-0403, USA.
authors: Guido D
authors: GD
authors: Frey
authors: Vincent
authors: V
authors: Lavallo
authors: Bruno
authors: B
authors: Donnadieu
authors: Wolfgang W
authors: WW
authors: Schoeller
authors: Guy
authors: G
authors: Bertrand