The Gauche Effect in XCH 2 CH 2 X Revisited
We have quantum chemically investigated the rotational isomerism of 1,2-dihaloethanes XCH CH X (X = F, Cl, Br, I) at ZORA-BP86-D3(BJ)/QZ4P. Our Kohn-Sham molecular orbital (KS-MO) analyses reveal that hyperconjugative orbital interactions favor the gauche conformation in all cases (X = F-I), not onl...
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| Veröffentlicht in: | Chemphyschem 2021-04, Vol.22 (7), p.641-648 |
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| container_title | Chemphyschem |
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| creator | Rodrigues Silva, Daniela de Azevedo Santos, Lucas Hamlin, Trevor A Fonseca Guerra, Célia Freitas, Matheus P Bickelhaupt, F Matthias |
| description | We have quantum chemically investigated the rotational isomerism of 1,2-dihaloethanes XCH
CH
X (X = F, Cl, Br, I) at ZORA-BP86-D3(BJ)/QZ4P. Our Kohn-Sham molecular orbital (KS-MO) analyses reveal that hyperconjugative orbital interactions favor the gauche conformation in all cases (X = F-I), not only for X = F as in the current model of this so-called gauche effect. We show that, instead, it is the interplay of hyperconjugation with Pauli repulsion between lone-pair-type orbitals on the halogen substituents that constitutes the causal mechanism for the gauche effect. Thus, only in the case of the relatively small fluorine atoms, steric Pauli repulsion is too weak to overrule the gauche preference of the hyperconjugative orbital interactions. For the larger halogens, X⋅⋅⋅X steric Pauli repulsion becomes sufficiently destabilizing to shift the energetic preference from gauche to anti, despite the opposite preference of hyperconjugation. |
| doi_str_mv | 10.1002/cphc.202100090 |
| format | Article |
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CH
X (X = F, Cl, Br, I) at ZORA-BP86-D3(BJ)/QZ4P. Our Kohn-Sham molecular orbital (KS-MO) analyses reveal that hyperconjugative orbital interactions favor the gauche conformation in all cases (X = F-I), not only for X = F as in the current model of this so-called gauche effect. We show that, instead, it is the interplay of hyperconjugation with Pauli repulsion between lone-pair-type orbitals on the halogen substituents that constitutes the causal mechanism for the gauche effect. Thus, only in the case of the relatively small fluorine atoms, steric Pauli repulsion is too weak to overrule the gauche preference of the hyperconjugative orbital interactions. For the larger halogens, X⋅⋅⋅X steric Pauli repulsion becomes sufficiently destabilizing to shift the energetic preference from gauche to anti, despite the opposite preference of hyperconjugation.</description><identifier>ISSN: 1439-4235</identifier><identifier>EISSN: 1439-7641</identifier><identifier>DOI: 10.1002/cphc.202100090</identifier><identifier>PMID: 33555663</identifier><language>eng</language><publisher>Germany</publisher><ispartof>Chemphyschem, 2021-04, Vol.22 (7), p.641-648</ispartof><rights>2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1073-5d7eabb4dd72c931113cf20fc181340f0bcfceb4747c72832cf6a17f25dee39a3</citedby><cites>FETCH-LOGICAL-c1073-5d7eabb4dd72c931113cf20fc181340f0bcfceb4747c72832cf6a17f25dee39a3</cites><orcidid>0000-0002-2973-5321 ; 0000-0002-7492-1801 ; 0000-0003-4655-7747 ; 0000-0002-4040-1728 ; 0000-0002-8191-7130 ; 0000-0002-5128-1004</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33555663$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Rodrigues Silva, Daniela</creatorcontrib><creatorcontrib>de Azevedo Santos, Lucas</creatorcontrib><creatorcontrib>Hamlin, Trevor A</creatorcontrib><creatorcontrib>Fonseca Guerra, Célia</creatorcontrib><creatorcontrib>Freitas, Matheus P</creatorcontrib><creatorcontrib>Bickelhaupt, F Matthias</creatorcontrib><title>The Gauche Effect in XCH 2 CH 2 X Revisited</title><title>Chemphyschem</title><addtitle>Chemphyschem</addtitle><description>We have quantum chemically investigated the rotational isomerism of 1,2-dihaloethanes XCH
CH
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CH
X (X = F, Cl, Br, I) at ZORA-BP86-D3(BJ)/QZ4P. Our Kohn-Sham molecular orbital (KS-MO) analyses reveal that hyperconjugative orbital interactions favor the gauche conformation in all cases (X = F-I), not only for X = F as in the current model of this so-called gauche effect. We show that, instead, it is the interplay of hyperconjugation with Pauli repulsion between lone-pair-type orbitals on the halogen substituents that constitutes the causal mechanism for the gauche effect. Thus, only in the case of the relatively small fluorine atoms, steric Pauli repulsion is too weak to overrule the gauche preference of the hyperconjugative orbital interactions. For the larger halogens, X⋅⋅⋅X steric Pauli repulsion becomes sufficiently destabilizing to shift the energetic preference from gauche to anti, despite the opposite preference of hyperconjugation.</abstract><cop>Germany</cop><pmid>33555663</pmid><doi>10.1002/cphc.202100090</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-2973-5321</orcidid><orcidid>https://orcid.org/0000-0002-7492-1801</orcidid><orcidid>https://orcid.org/0000-0003-4655-7747</orcidid><orcidid>https://orcid.org/0000-0002-4040-1728</orcidid><orcidid>https://orcid.org/0000-0002-8191-7130</orcidid><orcidid>https://orcid.org/0000-0002-5128-1004</orcidid></addata></record> |
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| source | Wiley Online Library Journals Frontfile Complete |
| title | The Gauche Effect in XCH 2 CH 2 X Revisited |
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