Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes
Autor(a) principal: | |
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Data de Publicação: | 2019 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10174/26721 https://doi.org/10.1002/jcc.25793 |
Resumo: | Thirty‐six stable complexes of formic acid with formaldehydes and thioformaldehydes were determined on the potential energy surface, in which the XCHO···HCOOH complexes are found to be more stable than the XCHS···HCOOH counterparts, with X = H, F, Cl, Br, CH3, NH2. All complexes are stabilized by hydrogen bonds, and their contribution to the total stabilization energy of the complexes increases in going from C‐H···S to C‐H···O to O‐H···S and finally to O‐H···O. Remarkably, a significant blueshift of Csp2‐H bond by 81–96 cm−1 in the Csp2‐H···O hydrogen bond has hardly ever been reported, and a considerable redshift of O‐H stretching frequency by 206–544 cm−1 in the O‐H···O/S hydrogen bonds is also predicted. The obtained results in our present work and previous literatures support that a distance contraction and a stretching frequency blueshift of C‐H bond involving hydrogen bond depend mainly on its polarity and gas phase basicity of proton acceptor, besides the rearrangement of electron density due to complex formation. Markedly, we suggest the ratio of deprotonation enthalpy to proton affinity (R c) as an indicator to prospect for classification of hydrogen bonds. The symmetry adapted perturbation theory results show a larger role of attractive electrostatic term in XO‐n as compared to that in XS‐n and the electrostatic interaction is overwhelming dispersion or induction counterparts in stabilizing XO‐n and XS‐n, with n = 1, 2, 3. |
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Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydesblue‐shifting hydrogen bondSAPT2+ analysisstabilityNBOThirty‐six stable complexes of formic acid with formaldehydes and thioformaldehydes were determined on the potential energy surface, in which the XCHO···HCOOH complexes are found to be more stable than the XCHS···HCOOH counterparts, with X = H, F, Cl, Br, CH3, NH2. All complexes are stabilized by hydrogen bonds, and their contribution to the total stabilization energy of the complexes increases in going from C‐H···S to C‐H···O to O‐H···S and finally to O‐H···O. Remarkably, a significant blueshift of Csp2‐H bond by 81–96 cm−1 in the Csp2‐H···O hydrogen bond has hardly ever been reported, and a considerable redshift of O‐H stretching frequency by 206–544 cm−1 in the O‐H···O/S hydrogen bonds is also predicted. The obtained results in our present work and previous literatures support that a distance contraction and a stretching frequency blueshift of C‐H bond involving hydrogen bond depend mainly on its polarity and gas phase basicity of proton acceptor, besides the rearrangement of electron density due to complex formation. Markedly, we suggest the ratio of deprotonation enthalpy to proton affinity (R c) as an indicator to prospect for classification of hydrogen bonds. The symmetry adapted perturbation theory results show a larger role of attractive electrostatic term in XO‐n as compared to that in XS‐n and the electrostatic interaction is overwhelming dispersion or induction counterparts in stabilizing XO‐n and XS‐n, with n = 1, 2, 3.Journal of Computational Chemistry, Wiley2020-02-03T10:16:43Z2020-02-032019-03-24T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10174/26721https://doi.org/10.1002/jcc.25793http://hdl.handle.net/10174/26721https://doi.org/10.1002/jcc.25793engTrung, N. T., Khanh, P. N., Carvalho, A. J. P., & Nguyen, M. T. (2019). Remarkable shifts of C(sp2)‐H and O‐H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes. Journal of Computational Chemistry, 40(13), 1387–1400.1387–140040Journal of Computational ChemistryCQE - Centro de Química de Évorandndajpalace@uevora.ptnd305Trung, Nguyen TienKhanh, Pham NgocCarvalho, Alfredo J. PalaceNguyen, Minh Thoinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-01-03T19:21:41Zoai:dspace.uevora.pt:10174/26721Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T01:16:57.841782Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes |
title |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes |
spellingShingle |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes Trung, Nguyen Tien blue‐shifting hydrogen bond SAPT2+ analysis stability NBO |
title_short |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes |
title_full |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes |
title_fullStr |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes |
title_full_unstemmed |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes |
title_sort |
Remarkable shifts of C(sp2)-H and O-H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes |
author |
Trung, Nguyen Tien |
author_facet |
Trung, Nguyen Tien Khanh, Pham Ngoc Carvalho, Alfredo J. Palace Nguyen, Minh Tho |
author_role |
author |
author2 |
Khanh, Pham Ngoc Carvalho, Alfredo J. Palace Nguyen, Minh Tho |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Trung, Nguyen Tien Khanh, Pham Ngoc Carvalho, Alfredo J. Palace Nguyen, Minh Tho |
dc.subject.por.fl_str_mv |
blue‐shifting hydrogen bond SAPT2+ analysis stability NBO |
topic |
blue‐shifting hydrogen bond SAPT2+ analysis stability NBO |
description |
Thirty‐six stable complexes of formic acid with formaldehydes and thioformaldehydes were determined on the potential energy surface, in which the XCHO···HCOOH complexes are found to be more stable than the XCHS···HCOOH counterparts, with X = H, F, Cl, Br, CH3, NH2. All complexes are stabilized by hydrogen bonds, and their contribution to the total stabilization energy of the complexes increases in going from C‐H···S to C‐H···O to O‐H···S and finally to O‐H···O. Remarkably, a significant blueshift of Csp2‐H bond by 81–96 cm−1 in the Csp2‐H···O hydrogen bond has hardly ever been reported, and a considerable redshift of O‐H stretching frequency by 206–544 cm−1 in the O‐H···O/S hydrogen bonds is also predicted. The obtained results in our present work and previous literatures support that a distance contraction and a stretching frequency blueshift of C‐H bond involving hydrogen bond depend mainly on its polarity and gas phase basicity of proton acceptor, besides the rearrangement of electron density due to complex formation. Markedly, we suggest the ratio of deprotonation enthalpy to proton affinity (R c) as an indicator to prospect for classification of hydrogen bonds. The symmetry adapted perturbation theory results show a larger role of attractive electrostatic term in XO‐n as compared to that in XS‐n and the electrostatic interaction is overwhelming dispersion or induction counterparts in stabilizing XO‐n and XS‐n, with n = 1, 2, 3. |
publishDate |
2019 |
dc.date.none.fl_str_mv |
2019-03-24T00:00:00Z 2020-02-03T10:16:43Z 2020-02-03 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10174/26721 https://doi.org/10.1002/jcc.25793 http://hdl.handle.net/10174/26721 https://doi.org/10.1002/jcc.25793 |
url |
http://hdl.handle.net/10174/26721 https://doi.org/10.1002/jcc.25793 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Trung, N. T., Khanh, P. N., Carvalho, A. J. P., & Nguyen, M. T. (2019). Remarkable shifts of C(sp2)‐H and O‐H stretching frequencies and stability of complexes of formic acid with formaldehydes and thioformaldehydes. Journal of Computational Chemistry, 40(13), 1387–1400. 1387–1400 40 Journal of Computational Chemistry CQE - Centro de Química de Évora nd nd ajpalace@uevora.pt nd 305 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Journal of Computational Chemistry, Wiley |
publisher.none.fl_str_mv |
Journal of Computational Chemistry, Wiley |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799136652118982656 |