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DC Field | Value | Language |
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dc.citation.endPage | 13733 | - |
dc.citation.number | 20 | - |
dc.citation.startPage | 13722 | - |
dc.citation.title | PHYSICAL CHEMISTRY CHEMICAL PHYSICS | - |
dc.citation.volume | 20 | - |
dc.contributor.author | Kim, Dong Yeon | - |
dc.contributor.author | Yang, D. ChangMo | - |
dc.contributor.author | Madridejos, Jenica Marie L. | - |
dc.contributor.author | Hajibabaei, Amir | - |
dc.contributor.author | Baig, Chunggi | - |
dc.contributor.author | Kim, Kwang S. | - |
dc.date.accessioned | 2023-12-21T20:43:58Z | - |
dc.date.available | 2023-12-21T20:43:58Z | - |
dc.date.created | 2018-07-07 | - |
dc.date.issued | 2018-05 | - |
dc.description.abstract | Despite its key importance in carbene chemistry, the amphoteric (i. e., both nucleophilic and electrophilic) behavior of the divalent carbon atom (: C) in carbenes is not well understood. The electrostatic potential (EP) around : C is often incorrectly described by simple isotropic atomic charges (particularly, as in singlet CF2); therefore, it should be described by the multipole model, which can illustrate both negative and positive EPs, favoring the positively and negatively charged species that are often present around : C. This amphotericity is much stronger in the singlet state, which has more conspicuous anisotropic charge distribution than the triplet state; this is validated by the complexation structures of carbenes interacting with Na+, Cl-, H2O, and Ag+. From the study of diverse carbenes [including CH2, CLi2/CNa2, CBe2/CMg2, CF2/CCl2, C(BH2) 2/C(AlH2) 2, C(CH3) 2/C(SiH3) 2, C(NH2) 2/C(PH2) 2, cyclic systems of C(CH2) 2/C(CH) 2, C(BHCH) 2, C(CH2CH) 2/C(CHCH) 2, and C(NHCH) 2/C(NCH) 2], we elucidate the relationships between the electron configurations, electron accepting/donating strengths of atoms attached to : C, p conjugation, singlet-triplet energy gaps, anisotropic hard wall radii, anisotropic electrostatic potentials, and amphotericities of carbenes, which are vital to carbene chemistry. The (s 2, p 2 or sp) electronic configuration associated with : C on the : CA2 plane (where A is an adjacent atom) in singlet and triplet carbenes largely governs the amphoteric behaviors along the : C tip and : C face-on directions. The : C tip and : C face-on sites of s 2 singlet carbenes tend to show negative and positive EPs, favoring nucleophiles and electrophiles, respectively; meanwhile, those of p 2 singlet carbenes, such as very highly p-conjugated 5-membered cyclic C(NCH) 2, tend to show the opposite behavior. Open-shell sp singlet (such as highly p-conjugated 5-membered cyclic C(CHCH) 2) and triplet carbenes show less anisotropic and amphoteric behaviors. | - |
dc.identifier.bibliographicCitation | PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.20, no.20, pp.13722 - 13733 | - |
dc.identifier.doi | 10.1039/c8cp00457a | - |
dc.identifier.issn | 1463-9076 | - |
dc.identifier.scopusid | 2-s2.0-85047643238 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/24365 | - |
dc.identifier.url | http://pubs.rsc.org/en/Content/ArticleLanding/2018/CP/C8CP00457A#!divAbstract | - |
dc.identifier.wosid | 000433262300006 | - |
dc.language | 영어 | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Anisotropic and amphoteric characteristics of diverse carbenes | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Physical; Physics, Atomic, Molecular & Chemical | - |
dc.relation.journalResearchArea | Chemistry; Physics | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | QUANTUM-CHEMISTRY | - |
dc.subject.keywordPlus | STABLE CARBENES | - |
dc.subject.keywordPlus | FISCHER CARBENE | - |
dc.subject.keywordPlus | PI INTERACTIONS | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | SINGLET | - |
dc.subject.keywordPlus | BOND | - |
dc.subject.keywordPlus | N-HETEROCYCLIC CARBENES | - |
dc.subject.keywordPlus | AROMATIC INTERACTIONS | - |
dc.subject.keywordPlus | TRIPLET METHYLENE | - |
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