Ammonia N–H activation by a N,N′-diamidocarbene

Abstract

The synthesis and characterization of N,N'-dimesityl-4,6-diketo-5,5-dimethylpyrimidin-2-ylidene is reported; this crystalline N,N'-diamidocarbene was found to split ammonia and engage in other reactions not exhibited by typical N-heterocyclic carbenes.

Stable singlet carbenes as mimics for transition metal centers

“…Note that although di(amido)carbenes c DAC , react with CO and NH 3 (vide infra), they are inert towards hydrogen even under forcing conditions (65 atm H 2 , 200 °C). 25 …”

Bond Activation with an Apparently Benign Ethynyl Dithiocarbamate ArCCSC(S)NR2

“…Continuing our investigations, we observed that the very weakly acidic diethylamine and diethylphosphine are cleaved at room temperature, affording adducts 12 and 13, in 78 and 56 % yield, respectively [17] (Scheme 4). In contrast, phenylacetylene, which is more acidic, does not react with 1.…”

A theoretical study on the hydrogen adducts of diamidocarbenes and diaminocarbenes

“…(4) The ability of the hydrogen adduct 4H to store hydrogen is also enhanced with the substitution of electrondonating groups on N 2 and N 5 . [36][37][38][39]. For example, Lee et al [36] discovered that N,N′-diamidocarbenes are ambiphilic and can behave as electrophiles and nucleophiles.…”