Bonding and stability of dinitrogen-bonded donor base-stabilized Si(0)/Ge(0) species [(cAACMe-Si/Ge)2(N2)]: EDA-NOCV analysis.
RSC Adv
; 12(7): 4081-4093, 2022 Jan 28.
Article
em En
| MEDLINE
| ID: mdl-35425464
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 â N2). Two B-Dur further provide π-backdonations (B â 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 E[double bond, length as m-dash]E bond is thermodynamically more favourable (E = Si, Ge) over binding energy of N2 inbetween two cAAC-E units.
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MEDLINE
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En
Ano de publicação:
2022
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Article