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<p>Gas-phase B<sub><i>n</i></sub><sup>+</sup> monocations exhibit strong hydrophilicity due to the prototypical electron-deficiency of boron. Joint chemisorption experiment and first-principles theory investigations performed herein indicate that the experimentally known planar magic-number <i>C</i><sub>2<i>v</i></sub> B<sub>13</sub><sup>+</sup> can react with H<sub>2</sub>O at room temperature to form a series of quasi-planar aromatic boron water complexes <i>C</i><sub>1</sub> B<sub>13</sub>(H<sub>2</sub>O)<sup>+</sup> (<b>1</b>), <i>C</i><sub>2</sub> B<sub>13</sub>(H<sub>2</sub>O)<sub>2</sub><sup>+</sup> (<b>2</b>), and <i>C</i><sub>1</sub> B<sub>12</sub>H(H<sub>2</sub>O)<sup>+</sup> (<b>3</b>) analogous to benzene C<sub>6</sub>H<sub>6</sub>. Extensive theoretical calculations and analyses unveil their chemisorption pathways, bonding patterns, and more importantly, the effective in-phase LP(H<sub>2</sub>O:)→LV(B) orbital overlaps between the more electronegative O atom in H<sub>2</sub>O as lone-pair (LP) σ-donor and periphery electron-deficient B atoms in B<sub>13</sub><sup>+</sup> (B<sub>3</sub>@B<sub>10</sub><sup>+</sup>) and B<sub>12</sub>H<sup>+</sup> (B<sub>3</sub>@B<sub>9</sub>H<sup>+</sup>) with lone vacant (LV) orbitals as LP σ-acceptors, evidencing the existence of the newly proposed boron bonds in chemistry. A LP(H<sub>2</sub>O:)→LV(B) boron bond in these boron water complexes possesses about 15 ~ 20% of the dissociation energy of a typical O–B covalent bond. Boron bonds are expected to exist in a wide range of boron-based complex systems with typical molecular ligands like H<sub>2</sub>O, CO, and NH<sub>3</sub> as effective σ-donors.</p> Graphical Abstract <p>Joint chemisorption experiment and first-principles theory investigations indicate that B<sub>13</sub><sup>+</sup> monocation can react with H<sub>2</sub>O to form a series of quasi-planar aromatic boron water complexes <i>C</i><sub>1</sub> B<sub>13</sub>(H<sub>2</sub>O)<sup>+</sup>, <i>C</i><sub>2</sub> B<sub>13</sub>(H<sub>2</sub>O)<sub>2</sub><sup>+</sup>, and <i>C</i><sub>1</sub> B<sub>12</sub>H(H<sub>2</sub>O)<sup>+</sup> analogous to benzene, evidencing the existence of boron bonds in chemistry.</p> <p></p>

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Observation of Boron Bonds in Aromatic Boron Water Complexes B13(H2O)n+ (n = 1,2) and B12H(H2O)+ Analogous to Benzene

  • 期刊论文

  • 发表日期：

    2025年8月30日

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  • Ting Zhang,
  • Rui-Nan Yuan,
  • Qiang Chen,
  • Si-Dian Li

摘要

Gas-phase Bn+ monocations exhibit strong hydrophilicity due to the prototypical electron-deficiency of boron. Joint chemisorption experiment and first-principles theory investigations performed herein indicate that the experimentally known planar magic-number C2v B13+ can react with H2O at room temperature to form a series of quasi-planar aromatic boron water complexes C1 B13(H2O)+ (1), C2 B13(H2O)2+ (2), and C1 B12H(H2O)+ (3) analogous to benzene C6H6. Extensive theoretical calculations and analyses unveil their chemisorption pathways, bonding patterns, and more importantly, the effective in-phase LP(H2O:)→LV(B) orbital overlaps between the more electronegative O atom in H2O as lone-pair (LP) σ-donor and periphery electron-deficient B atoms in B13+ (B3@B10+) and B12H+ (B3@B9H+) with lone vacant (LV) orbitals as LP σ-acceptors, evidencing the existence of the newly proposed boron bonds in chemistry. A LP(H2O:)→LV(B) boron bond in these boron water complexes possesses about 15 ~ 20% of the dissociation energy of a typical O–B covalent bond. Boron bonds are expected to exist in a wide range of boron-based complex systems with typical molecular ligands like H2O, CO, and NH3 as effective σ-donors.

Graphical Abstract

Joint chemisorption experiment and first-principles theory investigations indicate that B13+ monocation can react with H2O to form a series of quasi-planar aromatic boron water complexes C1 B13(H2O)+, C2 B13(H2O)2+, and C1 B12H(H2O)+ analogous to benzene, evidencing the existence of boron bonds in chemistry.