Ab initio molecular orbital study of the hydroxygermylene potential energy surface

So, Suk Ping

doi:10.1021/j100179a029

Cited by 14 publications

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“…Our present results indicate that germanium is also reluctant to form double bonds with selenium which support the tendency of germanium to adopt divalent structures whenever such an alternative exists. The barriers for H 2 GeX → trans -HGe−XH isomerizations are relatively high (52.8 kcal/mol for X = S, 36.5 kcal/mol for X = O, and as we have found, 46.4 kcal/mol for X = Se); therefore, double-bonded H 2 GeX isomers should be at least kinetically stable and amenable for experimental study.…”

Section: Resultssupporting

confidence: 52%

“…For the title compounds, the earlier ab initio studies of the H 2 GeO potential energy surface (PES) at the SCF level , and on the MP2/3-21G* correlated level have revealed that hydroxygermylene is the global minimum, and trans -HGeOH has been found to be slightly more stable than cis -HGeOH. The later conclusion was obtained only after taking the electron-correlation energy into account.…”

Section: Introductionmentioning

confidence: 99%

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Comparative ab Initio Study of Molecular Structures and Relative Stabilities of Germanone, Germathione, Germaselenone, and Their Structural Isomers

et al. 1998

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The relative stabilities of the H2GeX, trans-HGeXH, and cis-HGeXH (X = O, S, Se) species and the transition states for H2GeSe ↔ trans-HGeSeH and trans-HGeSeH ↔ cis-HGeSeH isomerizations were investigated using post-Hartree−Fock ab initio methods. Geometry optimization and frequency calculations were performed at the HF, MP2, DFT, and QCISD(T) levels using TZP(2d,2p), TZP(2df,2pd), and TZP++(2df,2pd) basis sets. In the cases of oxygen and sulfur, the isomers H2GeO and H2GeS represent the structures with the highest energy, and the global minima corresponds to the trans-HGeSH and cis-HGeOH forms, respectively. In a more detailed study of the potential energy surface of the Ge[H2Se] system, we have found that the trans-HGeSeH structure is a global minimum separated at the QCISDT/TZP(2df,2pd) level by only 0.5 and 2.0 kcal/mol from H2GeSe and cis-HGSeH, respectively. In all cases the electron correlation energy plays a dominant role, and reliable assignment of the relative stability of these energetically close-lying isomers was possible using only higher levels of ab initio theory.

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Section: Resultssupporting

confidence: 52%

Section: Introductionmentioning

confidence: 99%

Comparative ab Initio Study of Molecular Structures and Relative Stabilities of Germanone, Germathione, Germaselenone, and Their Structural Isomers

et al. 1998

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“…Same results have also been found for this process in H 3 SiOH 6 and H 2 GeO. 27 In the study of reactions 1a and 1b, it has been found that the reaction of GeH 2 and H 2 O to form the H 2 GeOH 2 complex is barrierless, whereas the isomerization of H 2 GeOH 2 to H 3 -GeOH via a 1,2-H shift has an activation barrier. Thus, reaction 1b is the rate-determining step for the formation reaction of H 3 GeOH from GeH 2 and H 2 O.…”

Section: Resultssupporting

confidence: 61%

Ab Initio Molecular Orbital Study of the Reaction of GeH₂ with H₂O and Decomposition Reactions of H₃GeOH

2001

J. Phys. Chem. A

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The formation of H 3 GeOH from GeH 2 and H 2 O and its decomposition paths have been studied using the G2 molecular orbital method. It is predicted that GeH 2 reacts with H 2 O exothermically (by 10.0 kcal mol -1 ) without a barrier to form a nonplanar complex, H 2 GeOH 2 , which isomerizes via a 1,2-H shift to H 3 GeOH with a barrier of 28.3 kcal mol -1 . The backward isomerization requires an activation energy of 61.1 kcal mol -1 . In addition, direct decompositions of H 3 GeOH yielding H 3 GeO + H, H 3 Ge + OH, and H 2 GeOH + H are shown to have large endothermicities of 113.7, 102.4, and 84.9 kcal mol -1 , and those producing H 2 -GeO + H 2 and HGeOH + H 2 to have activation energies of 82.1 and 57.6 kcal mol -1 , respectively. Hence, H 3 GeOH is stable to the above decomposition processes unless its temperature is moderately high or above.

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“…2,14,15 Trinquier and So have investigated the structure of germanone and its derivatives using ab initio calculations. [16][17][18] They found trans-HGeOH to be 1.0 kcal mol À1 more stable than cis-HGeOH and 19.0 kcal mol À1 more stable than the germanones, H 2 Ge]O. Irrespective of the group 14 X 2 E]O systems being postulated as intermediates, the experimental structures of stannanone, H 2 Sn]O and plumbanone, H 2 Pb]O were reported a long time ago. These compounds are also prone to oligomerization and addition reactions.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of germanones: far removed from ketones – a computational study

2013

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The recently isolated heavy ketone (X 2 E]O; E ¼ Ge) shows interesting reactivity towards simple addition reactions that are unknown for the organic (E]C) ketones. Density Functional Theory (DFT) calculations elucidate the role of the central atom and the substituent effects on the addition of acetone, carbon dioxide and water to formaldehyde, acetone, 2,4-dimethyl-3-pentanone, diphenyl ketone and their heavier (Si, Ge) analogs. NBO analysis reveals a large charge separation for heavier analogs, thereby increasing their reactivity. The activation barriers are reduced by as much as $30.0 to 40.0 kcal mol À1 for the nucleophilic addition to the heavy ketones as (E ¼ Si and Ge) compared to those of an organic ketone. Comparably lower stability of the reactants and higher stability of the transition state lowers the barriers of addition reactions for the heavier ketones. Apart from a smaller barrier, the nucleophilic addition reactions which are unfavorable for ketones are favored by 20-40 kcal mol À1 for their silicon and germanium counterparts. Calculations predict that similar addition reactions must be feasible for silanones (X 2 Si]O) as well.

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Ab initio molecular orbital study of the hydroxygermylene potential energy surface

Cited by 14 publications

References 0 publications

Comparative ab Initio Study of Molecular Structures and Relative Stabilities of Germanone, Germathione, Germaselenone, and Their Structural Isomers

Comparative ab Initio Study of Molecular Structures and Relative Stabilities of Germanone, Germathione, Germaselenone, and Their Structural Isomers

Ab Initio Molecular Orbital Study of the Reaction of GeH₂ with H₂O and Decomposition Reactions of H₃GeOH

Reactivity of germanones: far removed from ketones – a computational study

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Ab initio molecular orbital study of the hydroxygermylene potential energy surface

Cited by 14 publications

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Comparative ab Initio Study of Molecular Structures and Relative Stabilities of Germanone, Germathione, Germaselenone, and Their Structural Isomers

Comparative ab Initio Study of Molecular Structures and Relative Stabilities of Germanone, Germathione, Germaselenone, and Their Structural Isomers

Ab Initio Molecular Orbital Study of the Reaction of GeH2 with H2O and Decomposition Reactions of H3GeOH

Reactivity of germanones: far removed from ketones – a computational study

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Ab Initio Molecular Orbital Study of the Reaction of GeH₂ with H₂O and Decomposition Reactions of H₃GeOH