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 SM ISO690:2012MOHAPATRA, Swagat Kumar, ZHANG, Yadong, SANDHU, Bhupinder, FONARI, Marina, TIMOFEEVA, Tatiana, MARDER, Seth R., BARLOW, Stephen V.. Synthesis, characterization, and crystal structures of molybdenum complexes of unsymmetrical electron-poor dithiolene ligands. In: Polyhedron, 2016, nr. 116, pp. 88-95. ISSN 0277-5387. DOI: https://doi.org/10.1016/j.poly.2016.04.025 |
| EXPORT metadate: Google Scholar Crossref CERIF DataCite Dublin Core |
  Polyhedron |
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| Numărul 116 / 2016 / ISSN 0277-5387 /ISSNe 1873-3719 | ||||||
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| DOI:https://doi.org/10.1016/j.poly.2016.04.025 | ||||||
| Pag. 88-95 | ||||||
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Mo(S2C2(CF3)2)3, 1a, has proven a useful p-dopant in organic electronics. To develop more soluble p-dopants, MoS92−was treated with alkynes CF3CCCO2Me and CF3CCCOCF3to give the dianions of the corresponding tris(dithiolene) complexes, 1b2−and 1c2−, respectively, which were then oxidized to neutral molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)-ethane-1,2-dithiolene], 1b, and molybdenum tris[1-(trifluoroethanoyl)-2-(trifluoromethyl)ethane-1,2-dithiolene], 1c, using NO+PF6−. The crystal structures of (NEt4+)21b2−, (NEt4+)21c2−, and neutral 1c have been determined. In all three cases, the metal coordination is approximately trigonal prismatic and the major isomer is cis (approximately C3v). The structure of 1b2−is distorted by a twist towards pseudo-octahedral coordination similar to that seen in structures of 1a2−and Mo(S2C2(CO2Me)2)32−, 1d2−, salts, and that of 1c exhibits marked folds between the planes formed by the ligand atoms and those formed by the Mo and coordinated S atoms, similar to those seen in the structure of 1a. On the other hand, the metal dithiolene core of 1c2−is essentially undistorted from C3vsymmetry. The oxidant strength of the neutral molecules increases in the order 1d < 1b < 1a < 1c, with the potentials ranging from −0.02 to +0.39 V versus the ferrocenium/ferrocene couple. |
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| Cuvinte-cheie Dithiolene, electrochemistry, molybdenum, Redox chemistry, Substituent effects |
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Dublin Core Export
<?xml version='1.0' encoding='utf-8'?> <oai_dc:dc xmlns:dc='http://purl.org/dc/elements/1.1/' xmlns:oai_dc='http://www.openarchives.org/OAI/2.0/oai_dc/' xmlns:xsi='http://www.w3.org/2001/XMLSchema-instance' xsi:schemaLocation='http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd'> <dc:creator>Mohapatra, S.</dc:creator> <dc:creator>Zhang, Y.</dc:creator> <dc:creator>Sandhu, B.</dc:creator> <dc:creator>Fonari, M.S.</dc:creator> <dc:creator>Timofeeva, T.V.</dc:creator> <dc:creator>Marder, S.</dc:creator> <dc:creator>Barlow, S.</dc:creator> <dc:date>2016-09-01</dc:date> <dc:description xml:lang='en'><p> </p><p>Mo(S<sub>2</sub>C<sub>2</sub>(CF<sub>3</sub>)<sub>2</sub>)<sub>3</sub>, 1a, has proven a useful p-dopant in organic electronics. To develop more soluble p-dopants, MoS<sub>9</sub><sup>2−</sup>was treated with alkynes CF<sub>3</sub>CCCO<sub>2</sub>Me and CF<sub>3</sub>CCCOCF<sub>3</sub>to give the dianions of the corresponding tris(dithiolene) complexes, 1b<sup>2−</sup>and 1c<sup>2−</sup>, respectively, which were then oxidized to neutral molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)-ethane-1,2-dithiolene], 1b, and molybdenum tris[1-(trifluoroethanoyl)-2-(trifluoromethyl)ethane-1,2-dithiolene], 1c, using NO<sup>+</sup>PF<sub>6</sub><sup>−</sup>. The crystal structures of (NEt<sub>4</sub><sup>+</sup>)<sub>2</sub>1b<sup>2−</sup>, (NEt<sub>4</sub><sup>+</sup>)<sub>2</sub>1c<sup>2−</sup>, and neutral 1c have been determined. In all three cases, the metal coordination is approximately trigonal prismatic and the major isomer is cis (approximately C<sub>3</sub><sub>v</sub>). The structure of 1b<sup>2−</sup>is distorted by a twist towards pseudo-octahedral coordination similar to that seen in structures of 1a<sup>2−</sup>and Mo(S<sub>2</sub>C<sub>2</sub>(CO<sub>2</sub>Me)<sub>2</sub>)<sub>3</sub><sup>2−</sup>, 1d<sup>2−</sup>, salts, and that of 1c exhibits marked folds between the planes formed by the ligand atoms and those formed by the Mo and coordinated S atoms, similar to those seen in the structure of 1a. On the other hand, the metal dithiolene core of 1c<sup>2−</sup>is essentially undistorted from C<sub>3</sub><sub>v</sub>symmetry. The oxidant strength of the neutral molecules increases in the order 1d < 1b < 1a < 1c, with the potentials ranging from −0.02 to +0.39 V versus the ferrocenium/ferrocene couple.</p></dc:description> <dc:identifier>10.1016/j.poly.2016.04.025</dc:identifier> <dc:source>Polyhedron (116) 88-95</dc:source> <dc:subject>Dithiolene</dc:subject> <dc:subject>electrochemistry</dc:subject> <dc:subject>molybdenum</dc:subject> <dc:subject>Redox chemistry</dc:subject> <dc:subject>Substituent effects</dc:subject> <dc:title>Synthesis, characterization, and crystal structures of molybdenum complexes of unsymmetrical electron-poor dithiolene ligands</dc:title> <dc:type>info:eu-repo/semantics/article</dc:type> </oai_dc:dc>
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