Stabilisation and reactivity studies of donor-base ligand-supported gallium-phosphides with stronger binding energy: a theoretical approach

Stabilizing the exotic chemical species possessing multiple bonds is often extremely challenging due to insufficient orbital overlap, especially involving one heavier element. Bulky aryl groups and/or carbene as ligand have previously stabilized the SiSi, GeGe, and BB triple bonds. Herein, theoretical calculations have been carried out to shed light on the stability and bonding of elusive silaboryne/germaboryne (Si/GeB triple bond) stabilized by donor base ligands ((cAAC)BE(Me)(L); E = Si, L = cAACMe, NHCMe, PMe3; E = Ge, L = cAACMe). The heavier analogues (Sn, Pb) have been further studied for comparison. Additionally, the effects of bulky substituents at the Si and N atoms on the structural parameters and stability of those species have been investigated. Energy decomposition analysis coupled with natural orbital for chemical valence (EDA‐NOCV; for Si) showed that cAAC/NHC ligands could stabilize the exotic BSi‐Me species more efficiently than PMe3 ligands. The BSi partial triple bond of the corresponding species possesses a mixture of one covalent electron sharing BSi σ‐bond and two dative π‐bonds (B ← Si, B → Si).

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Bonding and stability of elusive silaboryne (SiB) and germaboryne (GeB) with donor base ligands

Das

Devi

Suthar

et al. 2023

J Comput Chem

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Small molecule activation by sila/germa boryne species

Karnamkkott,

Das,

Mondal

et al. 2023

J Comput Chem

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The 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.

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Stabilisation and reactivity studies of donor-base ligand-supported gallium-phosphides with stronger binding energy: a theoretical approach

Abstract: Gallium phosphide is a three-dimensional polymeric material of hetero-diatomic GaP unit. Our studies reveal the synthetic viability of donor base-stabilised monomeric Ga–P compounds with stronger binding energy, and explore their reactivity with metal carbonyls.

Cited by 2 publications

References 78 publications

Bonding and stability of elusive silaboryne (SiB) and germaboryne (GeB) with donor base ligands

Bonding and stability of elusive silaboryne (SiB) and germaboryne (GeB) with donor base ligands

Small molecule activation by sila/germa boryne species

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