Affiliation:
1. UCR-CNRS Joint Research Chemistry Laboratory (UMI 2957), Department of Chemistry, University of California, Riverside, CA 92521–0403, USA.
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 H
2
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 NH
3
as well, a difficult task for transition metals because of the formation of Lewis acid-base adducts.
Publisher
American Association for the Advancement of Science (AAAS)
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4. A few species which are only stable in matrices at 10 to 80 K are also known to split H 2 : subvalent group 13 species ( 5 ) triplet carbenes ( 6 ) and the highly electrophilic singlet difluorovinylidene ( 7 ).
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