Planar Tetracoordinate Carbon versus Planar Tetracoordinate Boron: The Case of CB<sub>4</sub> and Its Cation

Cui, Zhong‐hua; Contreras, Maryel; Ye, Ding; Merino, Gabriel

doi:10.1021/ja203682a

Cited by 109 publications

(62 citation statements)

References 49 publications

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“…In contrast, SiAl 4 − and GeAl 4 − clusters are instead distorted pentagons with C 2v symmetry. A related cluster, CB 4 2−/− , has also been studied, and its structure is analogous to that of SiAl 4 − and GeAl 4 − 26 . It was then proclaimed that the square planar geometry was not adopted by the SiAl 4 − and GeAl 4 − clusters because Si and Ge are too big to fit in the Al 4 cycle.…”

Section: Introductionmentioning

confidence: 99%

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−

Alexandrova

Nayhouse

Huynh

et al. 2012

Phys. Chem. Chem. Phys.

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CAl4 2−/− (D4h, 1A1g) is a cluster ion that has been established to be planar, aromatic, and contain a tetracoordinate planar C atom. Valence isoelectronic substitution of C with Si and Ge in this cluster leads to a radical change of structure toward distorted pentagonal species. We find that this structural change goes together with the cluster acquiring partial covalency of bonding between Si/Ge and Al4, facilitated by hybridization of the atomic orbitals (AOs). Counter intuitively, for the AAl4 2−/− (A = C, Si, Ge) clusters, hybridization in the dopant atom is strengthened from C, to Si, and to Ge, even though typically AOs are more likely to hybridize if they are closer in energy (i.e. in earlier elements in the Periodic Table). The trend is explained by the better overlap of the hybrids of the heavier dopants with the orbitals of Al4. From the thus understood trend, it is inferred that covalency in such clusters can be switched off, by varying the relative sizes of the AOs of the main element and the dopant. Using this mechanism, we then successfully killed covalency in Si, and predicted a new aromatic cluster ion containing a tetracoordinate square planar Si, SiIn4 2−/−.

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Section: Introductionmentioning

confidence: 99%

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−

Alexandrova

Nayhouse

Huynh

et al. 2012

Phys. Chem. Chem. Phys.

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“…As shown in Figure 1, the carbon dopant coordinates with four Be atoms again in the Be n C (n = 7-12) clusters, in which the Be-C bond lengths are in the range 1.589-1.767 Å. Different from the well-known tetrahedral tetracoordinate and novel planar tetracoordinate C atom, [64] the pyramidal tetracoordinate carbon atom has been found in these structures. Besides, since hypercoordination of carbon is usually not favored, [65] the maximum coordination number of C is four in our study.…”

Section: Isomermentioning

confidence: 93%

The Influence of Carbon Doping on the Structures, Properties, and Stability of Beryllium Clusters

Zhang

Yang

et al. 2017

Eur J Inorg Chem

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The global minimum structures of the carbon‐doped Ben (n = 1–12) clusters are obtained at the B3PW91/6‐311+G(d) level and compared with those of pure beryllium clusters. It is found that the carbon dopant prefers to be located outside the host Ben cage and tends to be tetracoordinated. The evolution of the electronic and energetic properties of BenC is studied using the QCISD(T) method. Results show that the introduction of carbon doping strengthens intracluster interaction of beryllium clusters. Besides, the Be3C and Be8C clusters, with their particular stability, are considered as magic‐number clusters in the BenC series. Molecular‐orbital (MO) analysis indicates that both clusters have fully filled electron shells, whereas the contribution of the carbon atomic orbital leads to MO energy‐level disorder of the BenC clusters.

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“…Computations were carried out using Gaussian 03 and Gaussian 09 program packages. To systematically explore the potential energy surface (PES) of [Be,C,O,S], the grid‐based comprehensive isomeric search strategies were initially carried out at the B3LYP/6‐31G(d) level. Then, the optimized geometries and harmonic vibrational frequencies of the local minima and transition states were obtained at the B3LYP/6‐311+G(d) level.…”

Section: Methodsmentioning

confidence: 99%

Structures, energetics, and isomerism of [Be,C,O,S]: Stability of triply bonded sulfur

Cui

2013

Int J of Quantum Chemistry

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Multiply bonded sulfur has continued to attract attention both experimentally and theoretically. Triply sulfur-bonded compounds are still rare, due to either the lack of suitable generation precursors or the conversion instability toward doubly sulfur-bonded structures. A detailed computational study was performed on the structures and stability of various [Be,C,O,S] isomers at the coupled cluster singles doubles (triple excitations) (CCSD(T))/aug-cc-pVTZ//B3LYP/6-311þG(d)þZPVE level to predict intrinsically stable isomers with triply bonded sulfur. The molecular orbital, bond distance, and harmonic vibrational frequency analysis were carried out at aug-cc-pVTZ-B3LYP, M06-2X, and CCSD(T) levels to investigate the bonding nature of linear structures. It was shown that two low-lying isomers are linear SBeCO 01 (0.0 kcal/mol) and SBeOC 02 (15.7 kcal/mol), both of which possess the SBBe triple bonding. The Lewis acid-base association of SBe þ CO can barrierlessly form 01 and 02, with the former more abundant, while the insertion reaction of SCO þ Be might generate more 02 than 01 via photochemical processes. By contrast, formation of the SBC-bearing isomer SCBeO 04 (39.4 kcal/mol) seems unlikely due to its higher energy and less kinetic competition than that of 01 and 02, via either simple association or insertion reactions. The new stable isomers SBeCO 01 and SBeOC 02 add to the number of SBBe triply bonded species. Their unique structures and varied branching ratios under association and insertion processes deserve future experimental study.

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Planar Tetracoordinate Carbon versus Planar Tetracoordinate Boron: The Case of CB₄ and Its Cation

Cited by 109 publications

References 49 publications

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−

The Influence of Carbon Doping on the Structures, Properties, and Stability of Beryllium Clusters

Structures, energetics, and isomerism of [Be,C,O,S]: Stability of triply bonded sulfur

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Planar Tetracoordinate Carbon versus Planar Tetracoordinate Boron: The Case of CB4 and Its Cation

Cited by 109 publications

References 49 publications

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−

The Influence of Carbon Doping on the Structures, Properties, and Stability of Beryllium Clusters

Structures, energetics, and isomerism of [Be,C,O,S]: Stability of triply bonded sulfur

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Planar Tetracoordinate Carbon versus Planar Tetracoordinate Boron: The Case of CB₄ and Its Cation