First Principle Attempt towards the Thermodynamic Stability of Telluroformaldehyde and its Heavier Analogs: H(2-n)X(n)A=Te (X=H, F, Cl and Br; A=C, Si and Ge; n=0-2)

Ramasami, Ponnadurai; Jaufeerally, Naziah B.

doi:10.1016/j.procs.2013.05.245

Cited by 3 publications

(8 citation statements)

References 38 publications

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“…The experimentally synthesized Tbt(Tip)GevTe and Tbt-(Dis)GevTe germanetellones were optimized as singlets using the BP86/Def2-TZVP method for better comparison of their bond dissociation energy with those of the mono-substituted germanetellones. 23 The def2-TZVP triple split valence basis sets 52,53 with polarization functions and small core ECP functions for the Te atom were employed for these computations. The bond dissociation energies of Tbt(Tip)GevTe and Tbt-(Dis)GevTe were obtained from the difference in enthalpy at 298 K between the germanetellones and those of the Tbt(R)Ge (R = Tip and Dis) triplets and the Te atom in its triplet ground state via the dissociation reaction (I):…”

Section: Methodsmentioning

confidence: 99%

“…Natural Bond Orbital (NBO) [54][55][56] analyses for Tbt(Tip)-GevTe and Tbt(Dis)GevTe were performed by the BP86/Def2-TZVP method, to characterize the GevTe moiety for comparison with analogous investigations on the simple germanetellones. 23…”

Section: Methodsmentioning

confidence: 99%

“…Similarly, the π electron system in the valence isoelectronic H 2 GevTe was earlier reported to display Ge + -Te − character. 23…”

Section: Structural Parametersmentioning

confidence: 99%

“…In addition, the atomic partial charges from the NBO analysis are q(C) = −0.61 and q(Te) = +0.24 in telluroformaldehyde, while q(Ge) = +0.79 and q(Te) = −0.39 for germanetellone. 23 Thus, Fig. 3 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1 A' state of (NC) 2 GevTe, the 3 A'' state of (NC) 2 GevTe, the 2 B'' state of the (NC) 2 GevTe + cation, and the 2 A'' state of the (NC) 2 GevTe − anion.…”

Section: Ionization Potentialsmentioning

confidence: 99%

“…The thermodynamic properties of the XYAvTe (X, Y = H, F, Cl and Br; A = C, Si and Ge) molecules were further explored by studying their heats of formation and evaluating their bond strengths in terms of the σ-bond energies, π-bond energies and bond dissociation enthalpies using isodesmic reaction schemes. 23 The carbon-oxygen double bonds of ketones (R 2 CvO) make them among the most important organic molecules, from the chemical industry to bioscience. 24 However, attempts to synthesize and isolate heavy ketones have not always been successful, due to the polarity of the AvE bonds (A = Si, Ge and Sn, E = O, S, Se and Te) and the spontaneous intermolecular oligomerization or polymerization of the heavy ketones.…”

Section: Introductionmentioning

confidence: 99%

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Novel germanetellones: XYGeTe (X, Y = H, F, Cl, Br, I and CN) – structures and energetics. Comparison with the first synthetic successes

et al. 2014

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No stable germanetellone was described until Tbt(Dis)Ge=Te and Tbt(Tip)Ge=Te (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Dis = bis(trimethylsilyl)methyl and Tip = 2,4,6-triisopropylphenyl) were reported in 1997. Following these initial experiments, there has arisen considerable interest in Ge[double bond, length as m-dash]Te systems. An obvious question is: why have the simple XYGe=Te (X, Y = H, F, Cl, Br, I and CN) molecules not yet been isolated? In view of the present situation, theoretical information may be of great help for further advances in germanetellone chemistry. A systematic investigation of the XYGe=Te molecules is carried out using the second order Møller-Plesset perturbation theory (MP2) and density functional theory (DFT). The structures and energetics, including ionization potentials (IPad and IPad(ZPVE)), four different forms of neutral-anion separations (EAad, EAad(ZPVE), VEA and VDE) and the singlet-triplet gaps, are reported. The electronegativity (χ) reactivity descriptor for the halogens (F, Cl, Br and I) and the natural charge separations of the Ge=Te moiety are used to assess the interrelated properties of germanetellone and its derivatives. The results are analyzed, discussed and compared with analogous studies of telluroformaldehyde, silanetellone and their derivatives. The thermodynamic viabilities of some of the novel germanetellones have also been evaluated in terms of the bond dissociation enthalpies of Tbt(Dis)Ge=Te and Tbt(Tip)Ge=Te. The simple mono-substituted germanetellones appear to be slightly more thermodynamically favored than Tbt(Dis)Ge=Te and Tbt(Tip)Ge=Te, since the bond dissociation enthalpies of these kinetically stabilized germanetellones are about 28 and 51 kcal mol(-1) lower, respectively.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…Similarly, the π electron system in the valence isoelectronic H 2 GevTe was earlier reported to display Ge + -Te − character. 23…”

Section: Structural Parametersmentioning

confidence: 99%

Section: Ionization Potentialsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Novel germanetellones: XYGeTe (X, Y = H, F, Cl, Br, I and CN) – structures and energetics. Comparison with the first synthetic successes

et al. 2014

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Computational study on fused five membered heterocyclic compounds containing tertiary oxygen

Dai

Zhang

Piao

et al. 2017

Journal of Molecular Structure

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Journey through the Potential Energy Surfaces for the Isomerization and Decomposition Reactions of the Telluroformaldehyde Analogues: H₂A═Te and HFA═Te (A = C, Si, and Ge)

et al. 2013

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The unavailability of monomeric heavy ketone analogues has been ascribed to the evanescence of the very reactive A═E double bond (A and E are the heavier group 14 and group 16 elements, respectively). Can the isolation of any of the monomeric telluro-ketones be assisted by an energetic favorability on its potential energy surface (PES)? In this light, the reaction pathways for the isomerization and decomposition reactions of H2A═Te and HFA═Te (A = C, Si, and Ge) molecules on their singlet state PES have been studied using second-order Møller-Plesset perturbation theory (MP2). The barrier heights reported suggest that telluroformaldehyde, silanetellone, and germatellone are kinetically more resistant to unimolecular reactions than the corresponding lighter chalcogen analogues. However, upon replacing a hydrogen atom by fluorine, the barrier heights of most of the isomerization and decomposition reactions are lowered. Among the unimolecular reactions studied for the H2A═Te and HFA═Te (A = C, Si, and Ge) molecules, the decomposition of cis-FGeTeH into HF and GeTe is found to be the most facile reaction, with a barrier height of only 4.6 kcal/mol. We also predict the ground state telluro-ketones to be viable molecules, as they have no imaginary vibrational frequencies and their lowest vibrational frequencies are always >100 cm(-1). In view of the scarcity of information on the chemistry of the mentioned telluro-ketones, the molecular parameters of various isomers and decomposition products have been reported, and should be useful for future experimental investigations.

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First Principle Attempt towards the Thermodynamic Stability of Telluroformaldehyde and its Heavier Analogs: H(2-n)X(n)A=Te (X=H, F, Cl and Br; A=C, Si and Ge; n=0-2)

Cited by 3 publications

References 38 publications

Novel germanetellones: XYGeTe (X, Y = H, F, Cl, Br, I and CN) – structures and energetics. Comparison with the first synthetic successes

Novel germanetellones: XYGeTe (X, Y = H, F, Cl, Br, I and CN) – structures and energetics. Comparison with the first synthetic successes

Computational study on fused five membered heterocyclic compounds containing tertiary oxygen

Journey through the Potential Energy Surfaces for the Isomerization and Decomposition Reactions of the Telluroformaldehyde Analogues: H₂A═Te and HFA═Te (A = C, Si, and Ge)

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First Principle Attempt towards the Thermodynamic Stability of Telluroformaldehyde and its Heavier Analogs: H(2-n)X(n)A=Te (X=H, F, Cl and Br; A=C, Si and Ge; n=0-2)

Cited by 3 publications

References 38 publications

Novel germanetellones: XYGeTe (X, Y = H, F, Cl, Br, I and CN) – structures and energetics. Comparison with the first synthetic successes

Novel germanetellones: XYGeTe (X, Y = H, F, Cl, Br, I and CN) – structures and energetics. Comparison with the first synthetic successes

Computational study on fused five membered heterocyclic compounds containing tertiary oxygen

Journey through the Potential Energy Surfaces for the Isomerization and Decomposition Reactions of the Telluroformaldehyde Analogues: H2A═Te and HFA═Te (A = C, Si, and Ge)

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Journey through the Potential Energy Surfaces for the Isomerization and Decomposition Reactions of the Telluroformaldehyde Analogues: H₂A═Te and HFA═Te (A = C, Si, and Ge)