Bridging η2‐BO in B2(BO)3− and B3(BO)3− Clusters: Boronyl Analogs of Boranes

Zhai, Hua‐Jin; Guo, Jin‐Chang; Li, Si‐Dian; Wang, Lai-Sheng

doi:10.1002/cphc.201100553

Cited by 41 publications

(37 citation statements)

References 41 publications

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“…The boronyl (BO) group with a B≡ ≡O triple bond is isovalent to the cyano (CN) group, both of which are known as monovalent σ-radicals. [46][47][48]55 A variety of boron oxide clusters were studied in the past years, demonstrating that the BO group plays a key role in their structures and bonding. The ratio of B versus O represents a new parameter to alter and tune the properties of boron oxide clusters.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopy of B4O4−: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

Tian

Zhao

Chen

et al. 2015

The Journal of Chemical Physics

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Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B4O4 (0/-) clusters. The measured PES spectra of B4O4 (-) exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of Cs B4O4 (-) ((2)A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D2h B4O4 (-) ((2)B2g) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B2O2 core bonded with terminal BO and/or BO2 groups. The same Y-shaped and rhombic structures are also located for the B4O4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B4O4 (0/-) clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B4O4 (0/-) clusters. This work is the first experimental study on a molecular system with an o-bond.

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Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopy of B4O4−: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

Tian

Zhao

Chen

et al. 2015

The Journal of Chemical Physics

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“…30 The bridging B−Au distances are much longer, consistent with a 3c-2e B−Au−B bond. Natural bond orbital (NBO) analysis confirms the highly covalent B−Au bonding, 50 20 The B−Au bonding in B 6 Au n − and B 6 Au n (n = 1−3) also closely parallels the B−(BO) bonding in boron oxide clusters [53][54][55] in terms of the terminal and bridging bonds, because Au and BO are both monovalent σ ligands analogous to H.…”

Section: B On the Vibrational Structuresmentioning

confidence: 83%

On the structures and bonding in boron-gold alloy clusters: B6Aun− and B6Aun (n = 1−3)

Chen

Zhai

et al. 2013

The Journal of Chemical Physics

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Photoelectron spectroscopy and density-functional theory are combined to investigate the electronic and structural properties of a series of B-Au alloy clusters: B6Aun(-) and B6Aun (n = 1-3). Rich spectral features are observed for each species, and vibrational structures are resolved for numerous detachment transitions of B6Au(-) and B6Au2(-). Electron affinities of B6Aun (n = 1-3) are evaluated to be 2.70 ± 0.03, 2.91 ± 0.02, and 3.21 ± 0.05 eV, respectively. Global structural searches are performed for both the anions and their neutrals. The calculated electronic binding energies are compared with experimental measurements to establish the anion global-minimum structures and their corresponding neutral states. The ground-state structures of these clusters are shown to be planar or quasi-planar with an elongated B6 core, to which the first and second Au atoms are bonded terminally and the third Au in a bridging position. All three anion clusters are π antiaromatic. Natural bond orbital analyses show that the B-Au bonding is highly covalent, providing new examples for the Au∕H analogy in Au alloy clusters.

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“…The sandwich structural pattern developed in this work expands the transition-metal complexes by introducing inorganic C 2v B 4 S 4 (1, [21] B(BS) 4 -, [8] and B 2 (BS) 6 . [22] These boron-rich boron sulfides proved to possess similar geometric structures with their oxide counterparts: BO, BO 2 -, B(BO) 2 -, B(BO) 3 -, [4,7,9,12] B(BO) 4 -, [8] and B 2 (BO) 6 . [22] It was also revealed that boron sulfide clusters favor the formation of the B≡S groups and there is a BS/H isolobal analogy similar to that of BO/H.…”

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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Bridging η²‐BO in B₂(BO)₃⁻ and B₃(BO)₃⁻ Clusters: Boronyl Analogs of Boranes

Cited by 41 publications

References 41 publications

Photoelectron spectroscopy of B4O4−: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

Photoelectron spectroscopy of B4O4−: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

On the structures and bonding in boron-gold alloy clusters: B6Aun− and B6Aun (n = 1−3)

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

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Bridging η2‐BO in B2(BO)3− and B3(BO)3− Clusters: Boronyl Analogs of Boranes

Cited by 41 publications

References 41 publications

Photoelectron spectroscopy of B4O4−: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

Photoelectron spectroscopy of B4O4−: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

On the structures and bonding in boron-gold alloy clusters: B6Aun− and B6Aun (n = 1−3)

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

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Bridging η²‐BO in B₂(BO)₃⁻ and B₃(BO)₃⁻ Clusters: Boronyl Analogs of Boranes

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