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Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered
dc.contributor.author | Hart, Mason D. | |
dc.contributor.author | Meyers, John J., Jr. | |
dc.contributor.author | Wood, Zachary A. | |
dc.contributor.author | Nakakita, Toshinori | |
dc.contributor.author | Applegate, Jason C. | |
dc.contributor.author | Erickson, Nathan R. | |
dc.contributor.author | Gerasimchuk, Nikolay N. | |
dc.contributor.author | Barybin, Mikhail V. | |
dc.date.accessioned | 2022-01-07T21:14:39Z | |
dc.date.available | 2022-01-07T21:14:39Z | |
dc.date.issued | 2021-02-12 | |
dc.identifier.citation | Hart, M.D.; Meyers, J.J., Jr.; Wood, Z.A.; Nakakita, T.; Applegate, J.C.; Erickson, N.R.; Gerasimchuk, N.N.; Barybin, M.V. Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered. Molecules 2021, 26, 981. https://doi.org/10.3390/molecules26040981 | en_US |
dc.identifier.uri | http://hdl.handle.net/1808/32372 | |
dc.description.abstract | Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X2-azulene ligands (X = H, Me, CO2Et, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)5Cr(2-isocyano-1,3-X2-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime “workhorse” aryl isocyanide ligand in coordination chemistry. Single crystal X-ray crystallographic {Cr–CNAz bond distances}, cyclic voltametric {E1/2(Cr0/1+)}, 13C NMR {δ(13CN), δ(13CO)}, UV-vis {dπ(Cr) → pπ*(CNAz) Metal-to-Ligand Charge Transfer}, and FTIR {νN≡C, νC≡O, kC≡O} analyses of the [(OC)5Cr(2-isocyano-1,3-X2-azulene)] complexes provided a multifaceted, quantitative assessment of the π-acceptor/σ-donor characteristics of the above five 2-isocyanoazulenes. In particular, the following inverse linear relationships were documented: δ(13COtrans) vs. δ(13CN), δ(13COcis) vs. δ(13CN), and δ(13COtrans) vs. kC≡O,trans force constant. Remarkably, the net electron withdrawing capability of the 2-isocyano-1,3-dicyanoazulene ligand rivals those of perfluorinated isocyanides CNC6F5 and CNC2F3. | en_US |
dc.publisher | MDPI | en_US |
dc.rights | © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license. | en_US |
dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | en_US |
dc.subject | Chromium pentacarbonyl | en_US |
dc.subject | Isocyanide | en_US |
dc.subject | Azulene | en_US |
dc.subject | Back-bonding | en_US |
dc.subject | Metal-to-ligand charge transfer | en_US |
dc.subject | Voltammetry | en_US |
dc.title | Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered | en_US |
dc.type | Article | en_US |
kusw.kuauthor | Hart, Mason D. | |
kusw.kuauthor | Meyers, John J., Jr. | |
kusw.kuauthor | Wood, Zachary A. | |
kusw.kuauthor | Nakakita, Toshinori | |
kusw.kuauthor | Applegate, Jason C. | |
kusw.kuauthor | Erickson, Nathan R. | |
kusw.kuauthor | Barybin, Mikhail V. | |
kusw.kudepartment | Chemistry | en_US |
dc.identifier.doi | 10.3390/molecules26040981 | en_US |
kusw.oaversion | Scholarly/refereed, publisher version | en_US |
kusw.oapolicy | This item meets KU Open Access policy criteria. | en_US |
dc.identifier.pmid | PMC7918097 | en_US |
dc.rights.accessrights | openAccess | en_US |