Abstract
Activation of N_2 at an ambient condition and reduction to produce ammonia employing
metal-free catalyst is one of the grand scientific problems to date. An effective appetite
of carbenes towards molecular nitrogen proclaims their candidature as N_2 sequestering
agent. However, the sequestering process is associated with a high activation energy
barrier. Thus, to ameliorate the use of carbene for the N 2 activation process a Density
Functional Theory (DFT) based design is pursued. Through a systematic study, the
binding mechanism of the C − N bond between carbene and nitrogen is explored to
model efficient carbene. Additionally, Intrinsic Reaction Coordinate (IRC) geometry
traping followed by molecular orbital analysis was employed to explore the electronic
level reaction mechanism of diazo derivative formation. It is corroborated that in the
carbene − N_2 reaction, carbene operates as a σ -acceptor and π-donor where
the bonding and the back bonding processes take place before and after the
transition state of the reaction. With the aid of this knowledge, a model carbene is
designed and computationally tested for nitrogen activation and ammonia formation.
It is observed that the model carbene, 6^CN , is an efficient candidate for nitrogen
activation and ammonia synthesis in a catalytic way. These results may stimulate
future experimental inquisitions.
Supplementary materials
Title
Ammonia synthesis from molecular nitrogen at the metal-free condition
Description
Employing an appropriate carbene, molecular nitrogen may be sequestered and converted to ammonia in a suitable reduction condition. Carbene acts as a σ -acceptor and π-donor in this process. The electronic level investigation proclaimed that the bonding and the back bonding processes are not instantaneous. These two processes occur at different stages of the reaction. The bonding takes place before reaching the transition state while the back bonding occurs after the transition state which implies that these two processes are independent of each other.
Actions