Structural and energetic exploration of a boron‐rich sulfide cluster B<sub>6</sub>S

Tang, Xiao‐Yu; Cui, Zhong‐hua; Shao, Chang-bin; Ye, Ding

doi:10.1002/qua.23128

Cited by 13 publications

(2 citation statements)

References 66 publications

(118 reference statements)

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“…The connection of each transition state was determined by the intrinsic reaction coordinate (IRC) (Fukui, 1981) calculations. The effectiveness of such isomeric and TS search strategies has been confirmed in study of various small to medium-sized systems (Cui et al, 2011; Gao and Ding, 2012; Tang et al, 2012; Guo et al, 2013a,b, 2014; Zhang and Ding, 2014, 2015; He and Ding, 2016; Xu et al, 2017; Bo et al, 2019).…”

Section: Computational Detailsmentioning

confidence: 89%

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Xin

Han

et al. 2019

Front. Chem.

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Despite the great interest in energy storage application, stable neutral C n O n ( n > 1) structures either in thermodynamics or kinetics have yet been largely limited due to the rather high tendency to release the very stable CO molecule. The neutral cyclopropanetrione (C 3 O 3 ) cluster has long remained elusive since no isomer with sufficient kinetic stability has been found either experimentally or theoretically. In this work, we constructed the first global potential energy surface of singlet C 3 O 3 at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level, from which the kinetic stability of a wide range of C 3 O 3 isomers can be determined by investigating their isomerization and fragmentation pathways. Amongst, a three-membered ring structure 01 is the global C 3 O 3 isomer with a barrier of 10.6 kcal/mol at the sophisticated W1BD level. In particular, two carbene-type isomers 02 and 04 possess appreciable destruction barriers of 20.3 and 24.7 kcal/mol at W1BD, respectively. Thus, 02 and 04 can be useful building blocks for constructing larger high-energy density carbon-oxygen clusters. Moreover, with the carbene center, both might effectively functionalize various nano-materials while retaining the electrochemical active carbonyl and epoxyl moieties that are very desirable in alkali metal-ion batteries.

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Section: Computational Detailsmentioning

confidence: 89%

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Xin

Han

et al. 2019

Front. Chem.

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“…To determine the isomeric structures as many compounds as possible, we applied our locally developed “skeleton-ligand cluster-growth” method . First, the isomeric search of the small C 2 Al 4 core was undertaken at the B3LYP/6-31G(d) level via our “grid-based comprehensive isomeric strategy”, which has been successfully tested in our previous works. − Second, via the “cluster-growth pattern”, each optimized C 2 Al 4 core was saturated by hydrogen atoms one by one in the forms of terminal, bridge, and delta-bonding types. For each hydrogenated structure, B3LYP/6-31G(d) structural and frequency calculations were carried out before the next hydrogenation.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Theoretical Designs for Organoaluminum C₂Al₄R₄ with Well-Separated Al(I) and Al(III)

Xue

Sui

et al. 2017

ACS Omega

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It is well-known that the chemistry of aluminum is dominated by Al(III) in the +3 oxidation state. Only during the past 2 decades has the chemistry of Al(I) and Al(II) been rapidly developed. However, if Al(I) and Al(III) are combined, the inherently high reactivities of Al(I) and Al(III) mostly result in their coupling with each other or interacting with surrounding elements, which easily results in significant deactivation or quenching of the desired oxidation states, as in the case of reported mixed valent Al-compounds. In this article, we report an unprecedented type of organoaluminum system, C 2 Al 4 R 4 (R = H, SiH 3 , Si(C 6 H 5 ) 3 , Si i PrDis 2 , SiMe(Si t Bu 3 ) 2 ), whose lowest-energy structure, C 2 Al 4 R 4 - 01 , contains two Al(I) and two Al(III) atoms. The global nature and bonding motif of the parent C 2 Al 4 R 4 - 01 (R = H) were supported by an extensive global isomeric search, CBS-QB3 energy calculations, adaptive natural density partitioning, and bond order analysis. Interestingly and in sharp contrast to most organoaluminum species, C 2 Al 4 R 4 - 01 is associated with little multicenter bonding. C 2 Al 4 R 4 - 01 has a high feasibility of being observed either in the gas or condensed phases (with suitable substitutents). With well-separated Al(I) and Al(III), C 2 Al 4 R 4 - 01 (with suitable substitutents) could serve as the first Al/Al frustrated Lewis pair.

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Pentaatomic planar tetracoordinate silicon with 14 valence electrons: A large-scale global search of SiXnYmq (n + m = 4;q = 0, ±1, −2; X, Y = main group elements from H to Br)

2014

J. Comput. Chem.

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Designing and characterizing the compounds with exotic structures and bonding that seemingly contrast the traditional chemical rules are a never-ending goal. Although the silicon chemistry is dominated by the tetrahedral picture, many examples with the planar tetracoordinate-Si skeletons have been discovered, among which simple species usually contain the 17/18 valence electrons. In this work, we report hitherto the most extensive structural search for the pentaatomic ptSi with 14 valence electrons, that is, SiXnYm(q) (n + m = 4; q = 0, ±1, -2; X, Y = main group elements from H to Br). For 129 studied systems, 50 systems have the ptSi structure as the local minimum. Promisingly, nine systems, that is, Li3SiAs(2-), HSiY3 (Y = Al/Ga), Ca3SiAl(-), Mg4Si(2-), C2LiSi, Si3Y2 (Y = Li/Na/K), each have the global minimum ptSi. The former six systems represent the first prediction. Interestingly, in HSiY3 (Y = Al/Ga), the H-atom is only bonded to the ptSi-center via a localized 2c-2e σ bond. This sharply contradicts the known pentaatomic planar-centered systems, in which the ligands are actively involved in the ligand-ligand bonding besides being bonded to the planar center. Therefore, we proposed here that to generalize the 14e-ptSi, two strategies can be applied as (1) introducing the alkaline/alkaline-earth elements and (2) breaking the peripheral bonding. In light of the very limited global ptSi examples, the presently designed six systems with 14e are expected to enrich the exotic ptSi chemistry and welcome future laboratory confirmation.

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Structural and energetic exploration of a boron‐rich sulfide cluster B₆S

Cited by 13 publications

References 66 publications

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Theoretical Designs for Organoaluminum C₂Al₄R₄ with Well-Separated Al(I) and Al(III)

Pentaatomic planar tetracoordinate silicon with 14 valence electrons: A large-scale global search of SiXnYmq (n + m = 4;q = 0, ±1, −2; X, Y = main group elements from H to Br)

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Structural and energetic exploration of a boron‐rich sulfide cluster B6S

Cited by 13 publications

References 66 publications

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Theoretical Designs for Organoaluminum C2Al4R4 with Well-Separated Al(I) and Al(III)

Pentaatomic planar tetracoordinate silicon with 14 valence electrons: A large-scale global search of SiXnYmq (n + m = 4;q = 0, ±1, −2; X, Y = main group elements from H to Br)

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Structural and energetic exploration of a boron‐rich sulfide cluster B₆S

Theoretical Designs for Organoaluminum C₂Al₄R₄ with Well-Separated Al(I) and Al(III)