A Computational Study of the Proton-Transfer Chemistry of the Silaformyl Anion

Rusho, Jon; Gordon, Mark S.; Damrauer, Niels H.; Damrauer, Robert

doi:10.1021/ja9722077

Cited by 7 publications

(11 citation statements)

References 27 publications

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“…22,23 At the CCSD(T)/6-311++G(2df,2pd) level of theory, HSiOH is virtually isoenergetic with H 2 SiO. 23 Therefore, it is of interest to determine the relative energies of titanone and its divalent isomer HTiOH. HTiOH has a linear structure in all states investigated at all levels of theory used in this work (See Table 4).…”

Section: Resultsmentioning

confidence: 99%

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Ab Initio Molecular Orbital Study of TiH₂O and TiH₃OH

Kudo

Gordon

1998

J. Phys. Chem. A

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Ab initio electronic structure calculations are reported for TiH2O and TiH3OH, the simplest prototypical molecules containing TiO and Ti−O bonds, respectively, with particular focus on the unimolecular decomposition mechanisms of TiH3OH and the isomerization of TiH2O. The equilibrium structures in the ground and lowest excited states and the potential energy surfaces for various unimolecular decomposition reactions are investigated, with the effects of electron correlation included. At the highest levels of theory (multiconfigurational wave functions augmented by second-order perturbation theory), singlet TiH2O is predicted to be the global minimum on its potential energy surface, and TiH3OH is predicted to be stable to unimolecular decomposition. Disciplines Chemistry CommentsReprinted (adapted) Ames, Iowa 50011-2030 ReceiVed: April 10, 1998 In Final Form: June 5, 1998 Ab initio electronic structure calculations are reported for TiH 2 O and TiH 3 OH, the simplest prototypical molecules containing TidO and Ti-O bonds, respectively, with particular focus on the unimolecular decomposition mechanisms of TiH 3 OH and the isomerization of TiH 2 O. The equilibrium structures in the ground and lowest excited states and the potential energy surfaces for various unimolecular decomposition reactions are investigated, with the effects of electron correlation included. At the highest levels of theory (multiconfigurational wave functions augmented by second-order perturbation theory), singlet TiH 2 O is predicted to be the global minimum on its potential energy surface, and TiH 3 OH is predicted to be stable to unimolecular decomposition.

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Section: Resultsmentioning

confidence: 99%

“…Hydroxysilylene (HSiOH), the divalent isomer of silanone, is known to be competitive in stability with silanone. , At the CCSD(T)/6-311++G(2df,2pd) level of theory, HSiOH is virtually isoenergetic with H 2 SiO . Therefore, it is of interest to determine the relative energies of titanone and its divalent isomer HTiOH.…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Molecular Orbital Study of TiH₂O and TiH₃OH

Kudo

Gordon

1998

J. Phys. Chem. A

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“…Unlike acetylene, however, HSiCH has a nonlinear trans geometry. Unlike HSiOH, no cis isomer can be found …”

Section: Resultsmentioning

confidence: 99%

Computational Study of the Proton-Transfer Chemistry of the Silaacetylide Anion

Rusho¹,

Gordon²,

Damrauer³

et al. 1998

Organometallics

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Reactions involving two [H,C,Si]- anions with the protonated neutral analogues (HSiCH, H2CSi, and H2SiC) have been studied. Calculations through fourth-order perturbation theory (MP4) suggest possible routes for single-proton transfer between the silaacetylide [HCSi]- anion and neutral species. Various important reaction paths for proton-transfer reactions and internal rearrangements of ion−molecule complexes are discussed. Accurate estimates of the acidity of HSiCH and H2SiC are presented and discussed in light of earlier experimental studies.

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“…More recent computational studies of proton-transfer reactions of HSiO -and CO 2 have been reported. 146,147 The silaacetone anion (eq 17), although not studied in the FA, is also of interest because the the chemical reactivity and property comparisons with acetone enolate. 125,126 An example is its reaction with CO 2 , in which CH 3 SiO 2 -and ketene are formed.…”

Section: Paths C and D To Alkyl Cleavage And Proton Abstractionmentioning

confidence: 99%

“…The large hydride affinity of SiO, much larger than that of CO (∼8 kcal/mol), indicates a greater “willingness” of SiO to disturb its π-bonding (Table ). More recent computational studies of proton-transfer reactions of HSiO - and CO 2 have been reported. , …”

Section: Organometallics: Group 14 Ion−molecule Chemistrymentioning

confidence: 99%

Organometallic Chemistry in the Flowing Afterglow: A Review

Damrauer

2004

Organometallics

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The flowing afterglow technique, among the various mass spectroscopic methods that have been used to study ions and ion−molecule reactions in the gas phase, has provided a number of interesting results in organometallic chemistry. The flowing afterglow technique is particularly suited for the investigation of thermally relaxed species, since ions and ion−molecule reactions are carried out in a pressure regime where multiple collisions with inert gases occur. Many of these studies are reviewed in this paper, with particular emphasis on anionic organometallic chemistry.

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A Computational Study of the Proton-Transfer Chemistry of the Silaformyl Anion

Cited by 7 publications

References 27 publications

Ab Initio Molecular Orbital Study of TiH₂O and TiH₃OH

Ab Initio Molecular Orbital Study of TiH₂O and TiH₃OH

Computational Study of the Proton-Transfer Chemistry of the Silaacetylide Anion

Organometallic Chemistry in the Flowing Afterglow: A Review

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A Computational Study of the Proton-Transfer Chemistry of the Silaformyl Anion

Cited by 7 publications

References 27 publications

Ab Initio Molecular Orbital Study of TiH2O and TiH3OH

Ab Initio Molecular Orbital Study of TiH2O and TiH3OH

Computational Study of the Proton-Transfer Chemistry of the Silaacetylide Anion

Organometallic Chemistry in the Flowing Afterglow: A Review

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Ab Initio Molecular Orbital Study of TiH₂O and TiH₃OH

Ab Initio Molecular Orbital Study of TiH₂O and TiH₃OH