Silicon-aryl cooperative activation of ammonia.

Herein, we report the reactivity of N-heterocyclic carbene stabilized silylene-phosphinidene IDippPSi(TMS)SiTol (IDipp = 1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) with ammonia, which results in an intermolecular 1,5-hydroamination and dearomatization of the NHC wingtip. DFT calculations reveal an unprecedented mechanism involving ammonia coordination to the silicon center, Meisenheimer-type complex formation, and a proton abstraction by the dearomatized aryl moiety.

Isolation of a NHC-stabilized heavier nitrile and its conversion into an isonitrile analogue.

Nitriles (R-C≡N) have been investigated since the late eighteenth century and are ubiquitous encounters in organic and inorganic syntheses. In contrast, heavier nitriles, which contain the heavier analogues of carbon and nitrogen, are sparsely investigated species. Here we report the synthesis and isolation of a phosphino-silylene featuring an N-heterocyclic carbene-phosphinidene and a highly sterically demanding silyl group as substituents.