Bonding and stability of dinitrogen-bonded donor base-stabilized Si(0)/Ge(0) species [(cAAC^Me-Si/Ge)<inf>2</inf>(N<inf>2</inf>)]: EDA-NOCV analysis

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 CcAAC 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. This journal is