Bonding and stability of dinitrogen-bonded donor base-stabilized Si(0)/Ge(0) species [(cAACMe–Si/Ge)2(N2)]: EDA-NOCV analysis

Abstract

Recently, dinitrogen (N₂) binding and its activation have been achieved by non-metal compounds like intermediate cAAC-borylene as (cAAC)₂(B-Dur)₂(N₂) [cAAC = cyclic alkyl(amino) carbene; Dur = aryl group, 2,3,5,6-tetramethylphenyl; B-Dur = borylene]. It has attracted a lot of scientific attention from different research areas because of its future prospects as a potent species towards the metal free reduction of N₂ into ammonia (NH₃) under mild conditions. Two (cAAC)(B-Dur) units, each of which possesses six valence electrons around the B-centre, are shown to accept σ-donations from the N₂ ligand (B ← N₂). Two B-Dur further provide π-backdonations (B → N₂) to a central N₂ ligand to strengthen the B–N₂–B bond, providing maximum stability to the compound (cAAC)₂(B-Dur)₂(N₂) since the summation of each pair wise interaction accounted for the total stabilization energy of the molecule. (cAAC)(B-Dur) unit is isolobal to cAAC–E (E = Si, Ge) fragment. Herein, we report on the stability and bonding of cAAC–E bonded N₂-complex (cAAC–E)₂(N₂) (1–2; Si, Ge) by NBO, QTAIM and EDA-NOCV analyses (EDA-NOCV = energy decomposition analysis coupled with natural orbital for chemical valence; QTAIM = quantum theory of atoms in molecule). Our calculation suggested that syntheses of elusive (cAAC–E)₂(N₂) (1–2; Si, Ge) species may be possible with cAAC ligands having bulky substitutions adjacent to the C_cAAC atom by preventing the homo-dimerization of two (cAAC)(E) units which can lead to the formation of (cAAC–E)₂. The formation of EE bond is thermodynamically more favourable (E = Si, Ge) over binding energy of N₂ inbetween two cAAC–E units.