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Noble Gas Compounds and Chemistry
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Noble Gas Compounds and Chemistry

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (31 August 2020) | Viewed by 26725

Special Issue Editor

Prof. Dr. Felice Grandinetti

E-Mail Website
Guest Editor
Department for Innovation in Biological, Agro-Food and Forest Systems (DIBAF), University of Tuscia, Via San Camillo De Lellis, Viterbo, Italy
Interests: noble-gas chemistry; gas-phase ion chemistry; computational chemistry; methods of bonding analysis; interstellar chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The present editorial project aims to provide a landscape view of the current different approaches to investigate noble gas compounds and chemistry.

Generally, noble gases are perceived as lowly reactive. In fact, only krypton and xenon produce compounds under ordinary (or nearly ordinary) conditions. However, in environments such as cold matrices and high-pressure devices or in gaseous phase, all noble gases, including helium, neon, and argon, really “forget” to be inert, and form a variety of molecules and ions. These species are investigated not only by experimental methods but also by theoretical calculations, extensively employed to aid the interpretation of the experiments and to explore aspects that escape the experimental work. This Special Issue wishes to illustrate the different approaches that are currently taken to explore the structure, bonding, and reactivity of noble gas compounds and to highlight the implications of their chemistry for different issues of fundamental and applied interest.

Prof. Felice Grandinetti
Guest Editor

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Keywords

  • Noble Gas Chemistry
  • Synthesis of Noble Gas Compounds
  • Gas-Phase Chemistry
  • Chemistry in Cold Matrices
  • Chemistry under High Pressures
  • Theoretical Calculations
  • Interstellar Chemistry

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Related Special Issue

Published Papers (7 papers)

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Research

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16 pages, 4066 KiB  
Article
On the Proton-Bound Noble Gas Dimers (Ng-H-Ng)+ and (Ng-H-Ng’)+ (Ng, Ng’ = He-Xe): Relationships between Structure, Stability, and Bonding Character
by Stefano Borocci, Felice Grandinetti and Nico Sanna
Molecules 2021, 26(5), 1305; https://doi.org/10.3390/molecules26051305 - 28 Feb 2021
Cited by 9 | Viewed by 2468
Abstract
The structure, stability, and bonding character of fifteen (Ng-H-Ng)+ and (Ng-H-Ng’)+ (Ng, Ng’ = He-Xe) compounds were explored by theoretical calculations performed at the coupled cluster level of theory. The nature of the stabilizing interactions was, in particular, assayed using a [...] Read more.
The structure, stability, and bonding character of fifteen (Ng-H-Ng)+ and (Ng-H-Ng’)+ (Ng, Ng’ = He-Xe) compounds were explored by theoretical calculations performed at the coupled cluster level of theory. The nature of the stabilizing interactions was, in particular, assayed using a method recently proposed by the authors to classify the chemical bonds involving the noble-gas atoms. The bond distances and dissociation energies of the investigated ions fall in rather large intervals, and follow regular periodic trends, clearly referable to the difference between the proton affinity (PA) of the various Ng and Ng’. These variations are nicely correlated with the bonding situation of the (Ng-H-Ng)+ and (Ng-H-Ng’)+. The Ng-H and Ng’-H contacts range, in fact, between strong covalent bonds to weak, non-covalent interactions, and their regular variability clearly illustrates the peculiar capability of the noble gases to undergo interactions covering the entire spectrum of the chemical bond. Full article
(This article belongs to the Special Issue Noble Gas Compounds and Chemistry)
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14 pages, 4027 KiB  
Article
Theoretical Prediction on the New Types of Noble Gas Containing Anions OBONgO− and OCNNgO− (Ng=He, Ar, Kr and Xe)
by Cheng-Cheng Tsai, Yu-Wei Lu and Wei-Ping Hu
Molecules 2020, 25(24), 5839; https://doi.org/10.3390/molecules25245839 - 10 Dec 2020
Cited by 4 | Viewed by 2649
Abstract
The fluorine-less noble gas containing anions OBONgO− and OCNNgO− have been studied by correlated electronic structure calculation and density functional theory. The obtained energetics indicates that for Ng=Kr and Xe, these anions should be kinetically stable at low temperature. The molecular [...] Read more.
The fluorine-less noble gas containing anions OBONgO− and OCNNgO− have been studied by correlated electronic structure calculation and density functional theory. The obtained energetics indicates that for Ng=Kr and Xe, these anions should be kinetically stable at low temperature. The molecular structures and electron density distribution suggests that these anions are stabilized by ion-induced dipole interactions with charges concentrated on the electronegative OBO and OCN groups. The current study shows that in addition to the fluoride ion, polyatomic groups with strong electronic affinities can also form stable noble gas containing anions of the type Y−…NgO. Full article
(This article belongs to the Special Issue Noble Gas Compounds and Chemistry)
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9 pages, 511 KiB  
Article
A Molecular Candle Where Few Molecules Shine: HeHHe+
by Ryan C. Fortenberry and Laurent Wiesenfeld
Molecules 2020, 25(9), 2183; https://doi.org/10.3390/molecules25092183 - 7 May 2020
Cited by 9 | Viewed by 3145
Abstract
HeHHe + is the only potential molecule comprised of atoms present in the early universe that is also easily observable in the infrared. This molecule has been known to exist in mass spectrometry experiments for nearly half-a-century and is likely present, but as-of-yet [...] Read more.
HeHHe + is the only potential molecule comprised of atoms present in the early universe that is also easily observable in the infrared. This molecule has been known to exist in mass spectrometry experiments for nearly half-a-century and is likely present, but as-of-yet unconfirmed, in cold plasmas. There can exist only a handful of plausible primordial molecules in the epochs before metals (elements with nuclei heavier than 4 He as astronomers call them) were synthesized in the universe, and most of these are both rotationally and vibrationally dark. The current work brings HeHHe + into the discussion as a possible (and potentially only) molecular candle for probing high-z and any metal-deprived regions due to its exceptionally bright infrared feature previously predicted to lie at 7.43 μ m. Furthermore, the present study provides new insights into its possible formation mechanisms as well as marked stability, along with the decisive role of anharmonic zero-point energies. A new entrance pathway is proposed through the triplet state ( 3 B 1 ) of the He 2 H + molecule complexed with a hydrogen atom and a subsequent 10.90 eV charge transfer/photon emission into the linear and vibrationally-bright 1 Σ g + HeHHe + form. Full article
(This article belongs to the Special Issue Noble Gas Compounds and Chemistry)
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8 pages, 368 KiB  
Article
Protonated and Cationic Helium Clusters
by Linnea Lundberg, Peter Bartl, Christian Leidlmair, Paul Scheier and Michael Gatchell
Molecules 2020, 25(5), 1066; https://doi.org/10.3390/molecules25051066 - 27 Feb 2020
Cited by 12 | Viewed by 3123
Abstract
Protonated rare gas clusters have previously been shown to display markably different structures compared to their pure, cationic counterparts. Here, we have performed high-resolution mass spectrometry measurements of protonated and pristine clusters of He containing up to 50 atoms. We identify notable differences [...] Read more.
Protonated rare gas clusters have previously been shown to display markably different structures compared to their pure, cationic counterparts. Here, we have performed high-resolution mass spectrometry measurements of protonated and pristine clusters of He containing up to 50 atoms. We identify notable differences between the magic numbers present in the two types of clusters, but in contrast to heavier rare gas clusters, neither the protonated nor pure clusters exhibit signs of icosahedral symmetries. These findings are discussed in light of results from heavier rare gases and previous theoretical work on protonated helium. Full article
(This article belongs to the Special Issue Noble Gas Compounds and Chemistry)
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Review

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20 pages, 4712 KiB  
Review
Noble Gas Bonding Interactions Involving Xenon Oxides and Fluorides
by Antonio Frontera
Molecules 2020, 25(15), 3419; https://doi.org/10.3390/molecules25153419 - 28 Jul 2020
Cited by 22 | Viewed by 4564
Abstract
Noble gas (or aerogen) bond (NgB) can be outlined as the attractive interaction between an electron-rich atom or group of atoms and any element of Group-18 acting as an electron acceptor. The IUPAC already recommended systematic nomenclature for the interactions of groups [...] Read more.
Noble gas (or aerogen) bond (NgB) can be outlined as the attractive interaction between an electron-rich atom or group of atoms and any element of Group-18 acting as an electron acceptor. The IUPAC already recommended systematic nomenclature for the interactions of groups 17 and 16 (halogen and chalcogen bonds, respectively). Investigations dealing with noncovalent interactions involving main group elements (acting as Lewis acids) have rapidly grown in recent years. They are becoming acting players in essential fields such as crystal engineering, supramolecular chemistry, and catalysis. For obvious reasons, the works devoted to the study of noncovalent Ng-bonding interactions are significantly less abundant than halogen, chalcogen, pnictogen, and tetrel bonding. Nevertheless, in this short review, relevant theoretical and experimental investigations on noncovalent interactions involving Xenon are emphasized. Several theoretical works have described the physical nature of NgB and their interplay with other noncovalent interactions, which are discussed herein. Moreover, exploring the Cambridge Structural Database (CSD) and Inorganic Crystal Structure Database (ICSD), it is demonstrated that NgB interactions are crucial in governing the X-ray packing of xenon derivatives. Concretely, special attention is given to xenon fluorides and xenon oxides, since they exhibit a strong tendency to establish NgBs. Full article
(This article belongs to the Special Issue Noble Gas Compounds and Chemistry)
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18 pages, 9442 KiB  
Review
Noble-Gas Chemistry More than Half a Century after the First Report of the Noble-Gas Compound
by Zoran Mazej
Molecules 2020, 25(13), 3014; https://doi.org/10.3390/molecules25133014 - 1 Jul 2020
Cited by 17 | Viewed by 5985
Abstract
Recent development in the synthesis and characterization of noble-gas compounds is reviewed, i.e., noble-gas chemistry reported in the last five years with emphasis on the publications issued after 2017. XeF2 is commercially available and has a wider practical application both in the [...] Read more.
Recent development in the synthesis and characterization of noble-gas compounds is reviewed, i.e., noble-gas chemistry reported in the last five years with emphasis on the publications issued after 2017. XeF2 is commercially available and has a wider practical application both in the laboratory use and in the industry. As a ligand it can coordinate to metal centers resulting in [M(XeF2)x]n+ salts. With strong Lewis acids, XeF2 acts as a fluoride ion donor forming [XeF]+ or [Xe2F3]+ salts. Latest examples are [Xe2F3][RuF6]·XeF2, [Xe2F3][RuF6] and [Xe2F3][IrF6]. Adducts NgF2·CrOF4 and NgF2·2CrOF4 (Ng = Xe, Kr) were synthesized and structurally characterized at low temperatures. The geometry of XeF6 was studied in solid argon and neon matrices. Xenon hexafluoride is a well-known fluoride ion donor forming various [XeF5]+ and [Xe2F11]+ salts. A large number of crystal structures of previously known or new [XeF5]+ and [Xe2F11]+ salts were reported, i.e., [Xe2F11][SbF6], [XeF5][SbF6], [XeF5][Sb2F11], [XeF5][BF4], [XeF5][TiF5], [XeF5]5[Ti10F45], [XeF5][Ti3F13], [XeF5]2[MnF6], [XeF5][MnF5], [XeF5]4[Mn8F36], [Xe2F11]2[SnF6], [Xe2F11]2[PbF6], [XeF5]4[Sn5F24], [XeF5][Xe2F11][CrVOF5]·2CrVIOF4, [XeF5]2[CrIVF6]·2CrVIOF4, [Xe2F11]2[CrIVF6], [XeF5]2[CrV2O2F8], [XeF5]2[CrV2O2F8]·2HF, [XeF5]2[CrV2O2F8]·2XeOF4, A[XeF5][SbF6]2 (A = Rb, Cs), Cs[XeF5][BixSb1-xF6]2 (x = ~0.37–0.39), NO2XeF5(SbF6)2, XeF5M(SbF6)3 (M = Ni, Mg, Zn, Co, Cu, Mn and Pd) and (XeF5)3[Hg(HF)]2(SbF6)7. Despite its extreme sensitivity, many new XeO3 adducts were synthesized, i.e., the 15-crown adduct of XeO3, adducts of XeO3 with triphenylphosphine oxide, dimethylsulfoxide and pyridine-N-oxide, and adducts between XeO3 and N-bases (pyridine and 4-dimethylaminopyridine). [Hg(KrF2)8][AsF6]2·2HF is a new example of a compound in which KrF2 serves as a ligand. Numerous new charged species of noble gases were reported (ArCH2+, ArOH+, [ArB3O4]+, [ArB3O5]+, [ArB4O6]+, [ArB5O7]+, [B12(CN)11Ne]−). Molecular ion HeH+ was finally detected in interstellar space. The discoveries of Na2He and ArNi at high pressure were reported. Bonding motifs in noble-gas compounds are briefly commented on in the last paragraph of this review. Full article
(This article belongs to the Special Issue Noble Gas Compounds and Chemistry)
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23 pages, 3551 KiB  
Review
Leading Interaction Components in the Structure and Reactivity of Noble Gases Compounds
by Francesca Nunzi, Giacomo Pannacci, Francesco Tarantelli, Leonardo Belpassi, David Cappelletti, Stefano Falcinelli and Fernando Pirani
Molecules 2020, 25(10), 2367; https://doi.org/10.3390/molecules25102367 - 20 May 2020
Cited by 20 | Viewed by 3242
Abstract
The nature, strength, range and role of the bonds in adducts of noble gas atoms with both neutral and ionic partners have been investigated by exploiting a fine-tuned integrated phenomenological–theoretical approach. The identification of the leading interaction components in the noble gases adducts [...] Read more.
The nature, strength, range and role of the bonds in adducts of noble gas atoms with both neutral and ionic partners have been investigated by exploiting a fine-tuned integrated phenomenological–theoretical approach. The identification of the leading interaction components in the noble gases adducts and their modeling allows the encompassing of the transitions from pure noncovalent to covalent bound aggregates and to rationalize the anomalous behavior (deviations from noncovalent type interaction) pointed out in peculiar cases. Selected adducts affected by a weak chemical bond, as those promoting the formation of the intermolecular halogen bond, are also properly rationalized. The behavior of noble gas atoms excited in their long-life metastable states, showing a strongly enhanced reactivity, has been also enclosed in the present investigation. Full article
(This article belongs to the Special Issue Noble Gas Compounds and Chemistry)
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