Small molecule activation by sila/germa boryne species

Abstract

AbstractThe inability of p‐block elements to participate in π‐backbonding restricts them from activating small molecules like CO, H2, and so forth. However, the development of the main group metallomimetics became a new pathway, where the main‐group elements like boron can bind and activate small molecules like CO and H2. The concept of the frustrated Lewis pair, Boron–Boron multiple bonds, and borylene are previously illustrated. Some of these reported classes of boron species can mimic the jobs of the metal complexes. Hence, we have theoretically studied the binding of CO/N2 molecules at B‐center of elusive species like sila/germa boryne stabilized by donor base ligands (cAAC)BE(Me)(L), where E  Si, L  cAACMe, NHCMe, PMe3, E  Ge, L  cAACMe and (NHCMe)BE(Me)(cAACMe)). The substitutional analogues of (cAACR)BSiR1(cAAC) and E  P, L  cAACMe) have been studied by density functional theory (DFT), natural bond orbital, QTAIM calculations and energy decomposition analysis (EDA) coupled with natural orbital for chemical valence (NOCV) analyses. The computed bond dissociation energy and inner stability analyses by the EDA‐NOCV method showed that the CO molecule can bind at the B‐center of the above‐mentioned species due to stronger σ‐donor ability while binding of N2 has been theoretically predicted to be weak. The energy barrier for the CO binding is estimated to be 13–14 kcal/mol by transition state calculation. The change of partial triple bond character to single bond nature of the BSi bond and the bending of CBSi bond angle of sila‐boryne species are the reason for the activation energy. Our study reveals the ability of such species to bind and activate the CO molecule to mimic the transition metal‐containing complexes. We have additionally shown that binding of Fe(CO)4 and Ni(CO)3 is feasible at Si‐center after binding of CO at the B‐center.