Missing Recipe in the Na‐B Bond in NaBH₃^–Cluster

Abstract

The multifaceted little Na−B bond in NaBH3‐ cluster has been the subject of many recent studies. Many proposals have been put forward for the complete understanding of the chemical bonding in NaBH3‐ cluster. However, none of the studies provided a complete picture. Herein, the missing recipe of the chemical bonding in NaBH3‐ cluster has been identified which completes the description. Our calculations reveal that the chemical bonding in NaBH3‐ cluster is more multifaceted than ever thought. Our finding suggests that the NaBH3‐ cluster features a Na−B one electron bond which is assisted by three 3‐centre‐2‐electron Na‐B−H bond. Detailed topological analyses of electron density and electron localization function at the correlated level reveal such a bonding situation. This missing 3‐centre‐2‐electron Na‐B−H bond completes the description of chemical bonding in NaBH3‐ cluster which is at‐per with the well established bonding scenario for electron deficient compounds. Similar bonding scenario is observed in KBH3−, CuBH3‐ and AuBH3− clusters, further lending support to the complete picture of bonding.

Can an alkalide act as a perfect Lewis base?

“…This has been recently highlighted by us in elucidating the complete bonding picture of the NaBH 3 − cluster. 25 However, no such monosynaptic V(E) and trisynaptic V(E, X, H) basins were observed for the studied clusters, indicating the absence of any biradicaloid character and reinforcing the role of H atoms in the E–X bond formation. All the EXH 2 − clusters studied here clearly reveal the formation of an unprecedented 2c–2e dative bond involving an alkalide as the Lewis base.…”

Classical versus Collective Interactions in Asymmetric Trigonal Bipyramidal Alkaline Metal–Boron Halide Complexes

“…After the discovery of NaBH 3 − in 2019 [1] the nature of Na…B bond initiated a debate that pushed the chemical bond theories to their edge [2–9] . A quick survey of the literature shows that similar species had been theoretically predicted a while before the experimental verification of NaBH 3 − and later a series of new complexes were predicted to share the same pattern of bonding [10–14] .…”

Anti-electrostatic cation⋯π-hole and cation⋯lp-hole interactions are stabilized via collective interactions

“…The experimental observation of NaBH 3 À in gas-phase in 2019 1 initiated a long-standing debate among the chemical community on the nature of the NaÁ Á ÁB bond in the molecule. [2][3][4][5][6][7][8][9] Besides NaBH 3 À , in recent years several other species have been investigated with bonding patterns akin to the molecule. [10][11][12][13][14] In a recent contribution we analyzed a series of over 100 molecules with the general formula MÁ Á ÁAX 3 , where M is a metal, A is C, B, or Al, in a tetra coordinate structure, and X represents various electron donating or withdrawing groups, Fig.…”