A theoretical study on novel neutral noble gas compound F<sub>4</sub>XeOsF<sub>4</sub>

Gao, Kunqi; Zhao, Rui; Sheng, Li

doi:10.1039/d0cp06450e

Cited by 5 publications

(5 citation statements)

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“…Moreover, in the same year, the fluorination of xenon , was achieved by two different groups of researchers. These reports initiated the xenon chemistry , and later on extended to general noble gas chemistry. − In this way, the field of noble gas chemistry had emerged as encouraging for several groups of scientists to unravel the unusual chemical bonding involved in noble gas compounds.…”

Section: Introductionmentioning

confidence: 99%

Unusual Spin States in Noble Gas Inserted Noble Metal Halocarbenes, FNgCM (Ng = Kr, Xe, Rn; M = Cu, Ag, Au)

et al. 2023

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Recent experimental detection of noble gas (Ng) inserted fluorocarbenes, viz., FKrCF and FXeCF, which were theoretically predicted by our group earlier and very recent experimental evidences on gold-halogen analogy motivated us to explore the possibility of the existence of noble gas inserted noble metal fluorocarbene, FNgCM (Ng = Kr, Xe, and Rn; M = Cu, Ag, and Au) molecules. Ab initio quantum chemical calculations have been performed to investigate structure, stability, vibrational frequency, charge distribution and bonding analysis of FNgCM molecules by employing DFT, MP2, and CCSD(T) methods. For the purpose of comparison FNgCH molecules have also been studied. One of the important outcomes of the study is that the predicted FNgCH, FNgCCu and FNgCAg molecules are more stable in their triplet electronic states, whereas the FNgCAu molecules are found to be more stable in their singlet potential energy surface, similar to the recently observed FNgCF (Ng = Kr and Xe) molecules, although the singlet state is the lowest energy state for all the precursor carbene molecules. The gold atom behaves as a better electron donor due to the pronounced relativistic effect as compared to hydrogen, copper and silver atoms, resulting in stabilization of the singlet carbene molecule indicating halogen like chemical behavior of gold. These molecules are found to be thermodynamically stable with respect to all plausible 2-body and 3-body dissociation channels, except the one that leads to the formation of the global minimum products. However, metastable nature of the predicted molecules has been proved by studying the saddle point corresponding to the transition from the minima to the global minimum products. Sufficient barrier heights provide the kinetic stability to the predicted FNgCM molecules, which prevent them from dissociating into their respective global minimum products. All the results clearly indicate that the F–Ng bond is mostly ionic in nature with certain amount of covalent character while Ng–C bond is found to be covalent in nature. Furthermore, atoms-in-molecule (AIM), energy decomposition analysis (EDA) and charge distribution analyses suggest that the predicted FNgCM molecules essentially exist in the form of [F]δ−[NgCM]δ+. The calculated results also indicate that it may be possible to prepare and characterize the predicted molecules by suitable experimental technique(s).

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Section: Introductionmentioning

confidence: 99%

Unusual Spin States in Noble Gas Inserted Noble Metal Halocarbenes, FNgCM (Ng = Kr, Xe, Rn; M = Cu, Ag, Au)

et al. 2023

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“…The domain of the noble gas chemistry has expanded after the discovery of the first stable molecule of argon (HArF) characterized using the infrared absorption spectroscopic technique supported by ab initio quantum chemical calculations by Räsänen and co-workers in 2000. , Following this revolutionized work, various noble gas-containing neutral and charged chemical compounds − ,− have been predicted theoretically and prepared via suitable experimental techniques. In general, these metastable compounds are obtained by inserting a noble gas atom into a stable molecule having either astronomical significance such as HCO + , HCS + , and HN 2 + or environmental importance such as HOX (X = F, Cl, and Br) and H 3 O + .…”

Section: Introductionmentioning

confidence: 99%

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

et al. 2022

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Recent theoretical prediction and experimental identification of fluorinated noble gas cyanides and isocyanides motivate us to explore a unique novel series of neutral noble gasinserted heavier cyanofluoride isomers, FNgYSi and FNgSiY (Ng = Kr, Xe, and Rn; Y = N and P), theoretically using quantum chemical calculations. The concerned minima and saddle point geometries have been optimized using DFT, MP2, and CCSD(T) methods. The precursor molecule FSiY is more stable than its isomer FYSi, and the stability order is found to be reversed after the insertion of a noble gas (Ng) atom into them which is in contrast to the previously reported FCN/FNC systems where the stability order in the precursors remains intact after the insertion of a Ng atom into them. The predicted FNgYSi molecules are metastable in nature as they are kinetically stable but thermodynamically unstable with respect to the global minima products (FYSi and Ng). All the calculations for the corresponding FNgSiY molecules clearly indicate that the less stable FNgSiY behaves similarly to the FNgYSi in all respects. The energetics, force constant, and spectroscopic data strongly reinforce the possibility of occurrence of these predicted FNgYSi and FNgSiY molecules which might be experimentally realized under suitable cryogenic condition(s).

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“…However, in the ground-breaking paper by Bartlett, the formation of [Xe + PtF 6 − ], 1,4 and subsequently the fluorination of xenon 5,6 was successfully accomplished. This discovery introduced the exciting world of noble gas chemistry, 7–15 which has been revisited several times in the past decades, resulting in the observation of numerous molecules containing chemically bonded noble gas atoms. 16–51…”

Section: Introductionmentioning

confidence: 99%

Existence of noble gas-inserted phosphorus fluorides: FNgPF₂and FNgPF₄with Ng–P covalent bond (Ng = Ar, Kr, Xe and Rn)

Kuntar

Ghosh

Ghanty

2022

Phys. Chem. Chem. Phys.

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A theoretical study on novel neutral noble gas compound F₄XeOsF₄

Abstract: The noble gas compound containing a triple bond of xenon and transition metal Os (i.e. F4XeOsF4, isomer A) is predicted using quantum-chemical calculations. At the MP2 level of theory, the...

Cited by 5 publications

References 73 publications

Unusual Spin States in Noble Gas Inserted Noble Metal Halocarbenes, FNgCM (Ng = Kr, Xe, Rn; M = Cu, Ag, Au)

Unusual Spin States in Noble Gas Inserted Noble Metal Halocarbenes, FNgCM (Ng = Kr, Xe, Rn; M = Cu, Ag, Au)

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

Existence of noble gas-inserted phosphorus fluorides: FNgPF₂and FNgPF₄with Ng–P covalent bond (Ng = Ar, Kr, Xe and Rn)

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A theoretical study on novel neutral noble gas compound F4XeOsF4

Abstract: The noble gas compound containing a triple bond of xenon and transition metal Os (i.e. F4XeOsF4, isomer A) is predicted using quantum-chemical calculations. At the MP2 level of theory, the...

Cited by 5 publications

References 73 publications

Unusual Spin States in Noble Gas Inserted Noble Metal Halocarbenes, FNgCM (Ng = Kr, Xe, Rn; M = Cu, Ag, Au)

Unusual Spin States in Noble Gas Inserted Noble Metal Halocarbenes, FNgCM (Ng = Kr, Xe, Rn; M = Cu, Ag, Au)

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

Existence of noble gas-inserted phosphorus fluorides: FNgPF2and FNgPF4with Ng–P covalent bond (Ng = Ar, Kr, Xe and Rn)

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A theoretical study on novel neutral noble gas compound F₄XeOsF₄

Existence of noble gas-inserted phosphorus fluorides: FNgPF₂and FNgPF₄with Ng–P covalent bond (Ng = Ar, Kr, Xe and Rn)