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Baig, Chunggi
Theoretical and Computational study of Polymers & Nanomaterials Lab
Research Interests
  • Multiscale simulation, polymer rheology, nonequilibrium molecular dynamics/monte carlo

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Anisotropic and amphoteric characteristics of diverse carbenes

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Title
Anisotropic and amphoteric characteristics of diverse carbenes
Author
Kim, Dong YeonYang, D. ChangMoMadridejos, Jenica Marie L.Hajibabaei, AmirBaig, ChunggiKim, Kwang S.
Issue Date
201805
Publisher
ROYAL SOC CHEMISTRY
Citation
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.20, no.20, pp.13722 - 13733
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.
URI
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DOI
http://dx.doi.org/10.1039/c8cp00457a
ISSN
1463-9076
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