Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/107225
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dc.contributor.authorXu, Xiangyaen
dc.contributor.authorKim, Seung Hyoen
dc.contributor.authorZhang, Xien
dc.contributor.authorDas, Atanu Kumaren
dc.contributor.authorHirao, Hajimeen
dc.contributor.authorHong, Soon Hyeoken
dc.date.accessioned2013-11-29T04:34:36Zen
dc.date.accessioned2019-12-06T22:27:04Z-
dc.date.available2013-11-29T04:34:36Zen
dc.date.available2019-12-06T22:27:04Z-
dc.date.copyright2013en
dc.date.issued2013en
dc.identifier.citationXu, X., Kim, S. H., Zhang, X., Das, A. K., Hirao, H., & Hong, S. H. (2013). Abnormal N-heterocyclic carbene gold(I) complexes : synthesis, structure, and catalysis in hydration of alkynes. Organometallics, 32(1), 164-171.en
dc.identifier.urihttps://hdl.handle.net/10356/107225-
dc.description.abstractTwo abnormal N-heterocyclic carbene (aNHC) gold(I) complexes, [(aNHC)AuCl], were prepared from C2-protected imidazolium salts. The air-stable complexes chloro(1-isopropyl-3-methyl-2,4-diphenylimidazol-5-ylidene)gold(I) (5) and chloro(1,4-diisopropyl-3-methyl-2-phenylimidazol-5-ylidene)gold(I) (6) were synthesized via transmetalation using (SMe2)AuCl and the corresponding silver salt such as [(aNHC)AgI] or [(aNHC)2Ag][I] and were fully characterized by NMR and mass spectroscopy and by X-ray crystallography. To investigate the structure, bonding, and catalytic activity of the aNHC-based Au complexes in comparison with their traditional NHC analogues, the sterically similar NHC-based Au complexes chloro(1,3-diisopropylimidazol-2-ylidene)gold(I) (7) and chloro(3-isopropyl-1-phenylimidazol-2-ylidene)gold(I) (8) were prepared from 1,3-diisopropylimidazolium iodide (3) and 3-isopropyl-1-phenylimidazolium iodide (4), respectively. X-ray crystallography and density functional theory (DFT) calculations showed that the aNHC complexes have longer Au–Ccarbene bond distances than the NHC complexes. Furthermore, DFT calculations predicted that, despite their longer Au–Ccarbene distances, aNHC complexes have stronger binding energies. It is suggested on the basis of additional theoretical analyses that these counterintuitive trends can be rationalized by considering individual factors that comprise the molecular interaction. The efficient back-donation of electrons and the smaller overlap repulsion in NHC complexes render the Au–Ccarbene distance shorter, whereas the stronger Au–Ccarbene bonding in the aNHC-Au complexes is attributed to the greater electrostatic attraction and the higher electron-donating ability of the carbene lone pair orbital. Catalytic activities of the NHC-based Au complexes were also compared in the alkyne hydration. Traditional NHC-based Au complexes exhibited higher efficiency in the reaction.en
dc.language.isoenen
dc.relation.ispartofseriesOrganometallicsen
dc.subjectDRNTU::Science::Chemistry::Organic chemistryen
dc.titleAbnormal N-heterocyclic carbene gold(I) complexes : synthesis, structure, and catalysis in hydration of alkynesen
dc.typeJournal Articleen
dc.contributor.schoolSchool of Physical and Mathematical Sciencesen
dc.identifier.doi10.1021/om3009603en
item.fulltextNo Fulltext-
item.grantfulltextnone-
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