Structures, Vibrational Frequencies, and Stabilities of Halogen Cluster Anions and Cations, Xn+/–, n = 3, 4, and 5

Thanthiriwatte, K. Sahan; Spruell, Jason M.; Dixon, David A.; Jenkins, H. Donald Brooke

doi:10.1021/ic501211f

Cited by 16 publications

(36 citation statements)

References 140 publications

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“…This compound is only the second example of a crystallographically characterized [I 5 ] + cation. The iodine–iodine bond lengths for the cation in [I 5 ][Me 3 NB 12 Cl 11 ] are longer than those in [I 5 ][AsF 6 ] and closer to those calculated for a free [I 5 ] + cation in the gas phase (Table S5 in the Supporting Information) . As was expected, the [Me 3 NB 12 Cl 11 ] − anion has a smaller influence on the structure of the [I 5 ] + cation and thus is more weakly coordinating than [AsF 6 ] − .…”

Section: Figuresupporting

confidence: 75%

The Me₃NB₁₂Cl₁₁^. Radical: A Strong One‐Electron Oxidizing Agent

Bertocco

Bolli

Derendorf

et al. 2016

Chemistry A European J

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Strong oxidizing agents often contain fluorine and are not compatible with substrates forming strong element-fluorine bonds. Therefore, there is need for new strong oxidizers. Cyclic voltammetric measurements on the weakly coordinating anion [Me NB Cl ] in liquid SO revealed an oxidation wave at +2.59 V versus Fc . The oxidation of Na[Me NB Cl ] with AsF in liquid sulfur dioxide gives the boron-cluster-based radical Me NB Cl as a dark blue solid in quantitative yield. The radical was characterized by vibrational, NMR, and EPR spectroscopy and by its crystal structure. To explore the potential of the radical Me NB Cl to act as a strong oxidizing agent, it was reacted with different compounds having high ionization energies. Thianthrene (ionization energy 7.8 eV) and hexabromobenzene (8.8 eV) were oxidized to the corresponding cations. The reaction with elemental iodine (9.3 eV) gave the [I ] cation. These reactive cations are stabilized in the solid state by the weakly coordinating anion [Me NB Cl ] , which was formed as a reduced product in the oxidation reactions.

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Section: Figuresupporting

confidence: 75%

The Me₃NB₁₂Cl₁₁^. Radical: A Strong One‐Electron Oxidizing Agent

Bertocco

Bolli

Derendorf

et al. 2016

Chemistry A European J

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“…Physical-chemical properties based on halogendoped triiodide anions are known. It demonstrates the extraordinary behavior of these anionic and cationic systems [32]. Within the scope of our work it may be of interest that under pressure even the stability of compounds as Na + Cl − changes and new materials with different stoichiometries can be presented at pressure as low as 25 GPa [33].…”

Section: Role Of Bond Symmetrization For a Specific Linearmentioning

confidence: 74%

A Molecular Description of Superconductivity of Sulfur Hydride and Related Systems under High-Pressure Conditions

Buck¹

2017

OJPC

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It has been shown that the recently discovered sulfur trihydride (H 3 S) can be considered as a superconductor with a transition temperature Tc of 203 Kelvin (K) at 155 GigaPascals (GPa). This is the highest Tc value reported for any superconductor. The established superconductivity occurs via the formation of a molecular system with sulfur atoms arranged on a body-centered cubic lattice. It has been generally accepted that the high Tc value is the result of an efficient electron-phonon interaction. The responsible substance formed by H 2 S under high pressure, may be considered as a compound with H 3 S stoichiometry creating an impressive network with hydrogens. We will focus on the hydrogen bonding between sulfur and hydrogens demonstrating a symmetrical arrangement. The geometry of the individual radical compound in relation to corresponding systems will be discussed. Ab initio calculations based on a linear three-center two-, three-and four-electron type of bonding clearly visualized in combination with the dynamics of the Van't Hoff concept, as described by us in various papers, give a good description of this exclusive network. We also discuss the superconductivity of related phosphorus hydrides and focus on the stability and geometrical differences with respect to the H 3 S system. These differences are significant, demonstrating the diversity in various structures in showing superconductivity.

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“…The structures and frequencies of some MX 3 species in the solid state are known, 6,7 providing indications that the X 3¯ moiety could be substantially altered by the presence of M + . Instead of the well-established symmetric and antisymmetric stretches 3,5 for the "free" X 3¯ anions, new modes with significant metal displacements may be involved in the MX 3 vibrations. Moreover, large red-shifts (7 -11%, about 20 -60 cm -1 , see Table S1 in the SI) from gas phase to argon matrices are highlighted by Jacox 8 for the ground state vibrational fundamentals of diatomic alkali metal halides (MX, M = Li, Na, K, Rb, Cs and X = F, Cl, Br, I).…”

Section: Introductionmentioning

confidence: 97%

Alkali-Metal Trihalides: M⁺X₃^– Ion Pair or MX–X₂ Complex?

et al. 2017

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The alkali-metal trihalides MX (M = Li, Na, K, Rb, and Cs; X = Cl, Br, and I) are systematically studied using coupled-cluster methods. Benchmarks using CCSD(T) against diatomic experimental results suggest satisfactory performance for the weighted core-valence basis sets (new basis sets for K, Rb, and Cs) selected for predicting reliable structures and harmonic vibrational frequencies. An isomer search using the B3LYP functional yields a planar, yet asymmetric T-shaped C structure as the global minimum for all MX species. Much higher level CCSD(T) computations show a moderate to strong distortion of the X anion by the M cation in the respective equilibrium geometries. Most obviously, for LiCl, the two Cl-Cl distances are separated by 0.786 Å. Even for CsI, the structure least distorted from the MX model, the two I-I distances differ by 0.243 Å. It does not take much energy to distort the parent anions along an antisymmetric stretch, so this is no surprise. The normal modes of vibration of the MX molecules are in better agreement with matrix isolation experiments than previous calculations. And these normal modes reveal that, instead of the well-established antisymmetric and symmetric stretches of the "free" X anions, relatively localized and mutually perturbed X-X and M-X stretches are calculated. The suggestion emerges that the MX system may be alternatively described as an MX-X complex rather than the MX ion pair. This perspective is supported by bonding analyses showing low electron densities at the bond critical points and natural bond orders between the MX and X moieties. The thermochemistry of fragmentations of MX to MX + X versus M + X also supports the alternative viewpoint of the bonding in this class of molecules.

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Structures, Vibrational Frequencies, and Stabilities of Halogen Cluster Anions and Cations, X_n^+/–, n = 3, 4, and 5

Cited by 16 publications

References 140 publications

The Me₃NB₁₂Cl₁₁^. Radical: A Strong One‐Electron Oxidizing Agent

The Me₃NB₁₂Cl₁₁^. Radical: A Strong One‐Electron Oxidizing Agent

A Molecular Description of Superconductivity of Sulfur Hydride and Related Systems under High-Pressure Conditions

Alkali-Metal Trihalides: M⁺X₃^– Ion Pair or MX–X₂ Complex?

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Structures, Vibrational Frequencies, and Stabilities of Halogen Cluster Anions and Cations, Xn+/–, n = 3, 4, and 5

Cited by 16 publications

References 140 publications

The Me3NB12Cl11. Radical: A Strong One‐Electron Oxidizing Agent

The Me3NB12Cl11. Radical: A Strong One‐Electron Oxidizing Agent

A Molecular Description of Superconductivity of Sulfur Hydride and Related Systems under High-Pressure Conditions

Alkali-Metal Trihalides: M+X3– Ion Pair or MX–X2 Complex?

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Structures, Vibrational Frequencies, and Stabilities of Halogen Cluster Anions and Cations, X_n^+/–, n = 3, 4, and 5

The Me₃NB₁₂Cl₁₁^. Radical: A Strong One‐Electron Oxidizing Agent

The Me₃NB₁₂Cl₁₁^. Radical: A Strong One‐Electron Oxidizing Agent

Alkali-Metal Trihalides: M⁺X₃^– Ion Pair or MX–X₂ Complex?