Chemical bonding in electron-deficient boron oxide clusters: core boronyl groups, dual 3c–4e hypervalent bonds, and rhombic 4c–4e bonds

Chen, Qiang; Lu, Hai‐Gang; Zhai, Hua‐Jin; Li, Si‐Dian

doi:10.1039/c4cp00406j

Cited by 34 publications

(68 citation statements)

References 35 publications

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“…26 We also predicted the viability of boronyl boroxine, D 3h B 6 The current C s B 4 O 4 + global-minimum structure also helps reinterpret the early experimental collisional activation spectrum. 26 We also predicted the viability of boronyl boroxine, D 3h B 6 The current C s B 4 O 4 + global-minimum structure also helps reinterpret the early experimental collisional activation spectrum.…”

Section: Introductionmentioning

confidence: 71%

On the structure and bonding in the B₄O₄⁺cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

Tian

You

et al. 2015

Phys. Chem. Chem. Phys.

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Boron oxide clusters offer intriguing molecular models for the electron-deficient system, in which the boronyl (BO) group plays a key role and the interplay between the localized BO triple bond and the multicenter electron delocalization dominates the chemical bonding. Here we report the structural, electronic, and bonding properties of the B4O4(+) cationic cluster on the basis of unbiased Coalescence Kick global-minimum searches and first-principles electronic structural calculations at the B3LYP and single-point CCSD(T) levels. The B4O4(+) cluster is shown to possess a Cs (1, (2)A') global minimum. It represents the smallest boron oxide species with a hexagonal boroxol (B3O3) ring as the core, terminated by a boronyl group. Chemical bonding analyses reveal double (π and σ) aromaticity in Cs B4O4(+), which closely mimics that in the 3,5-dehydrophenyl cation C6H3(+) (D3h, (1)A1'), a prototypical molecule with double aromaticity. Alternative D2h (2, (2)B3g) and C2v (3, (2)A1) isomeric structures of B4O4(+) are also analyzed, which are relevant to the global minima of B4O4 neutral and B4O4(-) anion, respectively. These three structural motifs vary drastically in terms of energetics upon changing the charge state, demonstrating an interesting case in which every electron counts. The calculated ionization potentials and electron affinities of the three corresponding neutral isomers are highly uneven, which underlie the conformational changes in the B4O4(+/0/-) series. The current work presents the smallest boron oxide species with a boroxol ring, establishes an analogy between boron oxides and the 3,5-dehydrophenyl cation, and enriches the chemistry of boron oxides and boronyls.

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Section: Introductionmentioning

confidence: 71%

On the structure and bonding in the B₄O₄⁺cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

Tian

You

et al. 2015

Phys. Chem. Chem. Phys.

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“…Such a nonbonding/bonding system is recently described as an o-bond. 46,48 The o-bond differs from a typical 4π antiaromatic system; the latter features an antibonding/bonding combination for the two π CMOs, which leads to a rectangular structural distortion. The HOMO of C 2v ( 1 A 1 ) is also localized around the tetracoordinate B atom, suggesting an approximate "B − " center.…”

Section: B Tetrahedral B 5 Omentioning

confidence: 98%

“…28 Subsequently, we reported a computational study on the structural and bonding properties of a series of B 3 O n −/0/+ (n = 2-4) clusters, as well as a joint experimental and theoretical study on the B 4 O 4 0/− clusters. 46,48 Now it is time to discuss the structural and bonding evolution along the whole B n O n (n = 1-6) series. Figure 7 summarizes the structures and cohesive energies of these clusters.…”

Section: Growth Pattern Of the Whole B N O N (N = 1-6) Seriesmentioning

confidence: 99%

A first-principles study on the B5O5+/0 and B5O5− clusters: The boron oxide analogs of C6H5+/0 and CH3Cl

Tian

You

et al. 2015

The Journal of Chemical Physics

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The concept of boronyl (BO) and the BO/H isolobal analogy build an interesting structural link between boron oxide clusters and hydrocarbons. Based upon global-minimum searches and first-principles electronic structural calculations, we present here the perfectly planar C2v B5O5 (+) (1, (1)A1), C2v B5O5 (2, (2)A1), and tetrahedral Cs B5O5 (-) (3, (1)A') clusters, which are the global minima of the systems. Structural and molecular orbital analyses indicate that C2v B5O5 (+) (1) [B3O3(BO)2 (+)] and C2v B5O5 (2) [B3O3(BO)2] feature an aromatic six-membered boroxol (B3O3) ring as the core with two equivalent boronyl terminals, similar to the recently reported boronyl boroxine D3h B6O6 [B3O3(BO)3]; whereas Cs B5O5 (-) (3) [B(BO)3(OBO)(-)] is characterized with a tetrahedral B(-) center, terminated with three BO groups and one OBO unit, similar to the previously predicted boronyl methane Td B5O4 (-) [B(BO)4 (-)]. Alternatively, the 1-3 clusters can be viewed as the boron oxide analogs of phenyl cation C6H5 (+), phenyl radical C6H5, and chloromethane CH3Cl, respectively. Chemical bonding analyses also reveal a dual three-center four-electron (3c-4e) π hyperbond in Cs B5O5 (-) (3). The infrared absorption spectra of B5O5 (+) (1), B5O5 (2), and B5O5 (-) (3) and anion photoelectron spectrum of B5O5 (-) (3) are predicted to facilitate their forthcoming experimental characterizations. The present work completes the BnOn (+/0/-) series for n = 1-6 and enriches the analogous relationship between boron oxides and hydrocarbons.

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“…A variety of boron oxide clusters have been studied in the past years. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Very recently, a new member of the "inorganic benzene" family, D 3h B 6 O 6 , has been discovered computationally, [17] which is a boron oxide analog of boroxine (B 3 O 3 H 3 ). The B 6 O 6 cluster features a boroxol B 3 O 3 ring as the structural core with three boronyl (BO) groups attached terminally, closely resembling boroxine and obtainable from the latter by isovalent BO/H substitution.…”

Section: Introductionmentioning

confidence: 99%

Binary B₄S₄ Rhombic Clusters as Promising Inorganic Ligands for Triple‐Decker Sandwich Complexes

Zhang

Dong

2016

Eur J Inorg Chem

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Abstract:Designing new forms of ligands and their sandwichtype analogs is the beginning of building multidecker metallic sandwich clusters and their infinite one-dimensional molecular wires. Here, we report on two binary B-S clusters: C 2v B 4 S 4 (1, 1 A 1 ) and D 2h B 4 S 4 -(2, 2 B 2u ) with rhombic B 2 S 2 as the core are their global minimum structures based upon global searches and electronic structure calculations at the B3LYP and coupledcluster theory [CCSD(T)] levels. The global-minimum structures 1 and 2 can be formulated as B 2 S 2 (BS) 2 and feature B 2 S 2 fourmembered rings as the core, with two -BS terminal groups attached terminally, closely resembling B 2 S 2 H 2 with a rhombic B 2 S 2 core and obtainable from the latter by isovalent BS/H substitution. Bonding analyses reveal a 4c-4e o-bond in C 2v B 4 S 4 (1, 1 A 1 ), which is 4π systems in the nonbonding/bonding com-

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Chemical bonding in electron-deficient boron oxide clusters: core boronyl groups, dual 3c–4e hypervalent bonds, and rhombic 4c–4e bonds

Cited by 34 publications

References 35 publications

On the structure and bonding in the B₄O₄⁺cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

On the structure and bonding in the B₄O₄⁺cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

A first-principles study on the B5O5+/0 and B5O5− clusters: The boron oxide analogs of C6H5+/0 and CH3Cl

Binary B₄S₄ Rhombic Clusters as Promising Inorganic Ligands for Triple‐Decker Sandwich Complexes

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Chemical bonding in electron-deficient boron oxide clusters: core boronyl groups, dual 3c–4e hypervalent bonds, and rhombic 4c–4e bonds

Cited by 34 publications

References 35 publications

On the structure and bonding in the B4O4+cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

On the structure and bonding in the B4O4+cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

A first-principles study on the B5O5+/0 and B5O5− clusters: The boron oxide analogs of C6H5+/0 and CH3Cl

Binary B4S4 Rhombic Clusters as Promising Inorganic Ligands for ­Triple‐Decker Sandwich Complexes

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On the structure and bonding in the B₄O₄⁺cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

On the structure and bonding in the B₄O₄⁺cluster: a boron oxide analogue of the 3,5-dehydrophenyl cation with p and s double aromaticity

Binary B₄S₄ Rhombic Clusters as Promising Inorganic Ligands for Triple‐Decker Sandwich Complexes