60633 20210121114542.0 doi 10.1002/zaac.201500566 sideral 92241 ART-2015-92241 eng (orcid)0000-0003-1707-3022 Casado, M.A. Universidad de Zaragoza Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands 2015 Access copy available to the general public Unrestricted Treatment of complex Cp2TiCl2] with the lithium salt of 2-hydroxypyridine afforded complex Cp2Ti(Opy)2] (1), whereas the same synthetic strategy applied to the analogous zirconium compound Cp2ZrCl2] did not worked. However, the use of the metallocene Cptt 2ZrMe2] with protic ligands allowed directing the reactivity towards protonation of the methyl groups attached to zirconium. To check this approach we reacted Cptt 2ZrMe2] with methanol affording complex Cptt 2ZrMe(OMe)] (2), which was characterized in situ by NMR techniques. In the same line, the reaction of Cptt 2ZrMe2] with 2-hydroxypyridine gave complex Cptt 2Zr(Me)(Opy)] (3)//forcing the conditions of this reaction did not lead to the expected complex Cptt 2Zr(Opy)2], most probably due to the steric hindrance exerted by the bulky cyclopentadienyl ligands. Further reactions of complex 3 with ligands having acidic protons also led to the recovery of the starting complex. However, when shifting to the bifunctional ligand 2, 6-dimercaptopyridine py(SH)2] a double protonation of the methyl ligands in Cptt 2ZrMe2] occurred, allowing the isolation of mononuclear complex Cptt 2Zr(¿S, ¿S, ¿N-pyS2)] (4), upon evolution of methane. The molecular structure of complex 4 was determined by X-ray methods, showing the zirconium atom in a highly distorted trigonal bipyramidal arrangement//structural parameters indicate a conventional Zr-N bond, but rather weak Zr-S interactions. info:eu-repo/grantAgreement/ES/DGA/E07 info:eu-repo/grantAgreement/ES/DGA/E70 info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2009-0050 info:eu-repo/grantAgreement/ES/MINECO/CTQ2012–35665 info:eu-repo/grantAgreement/ES/MINECO/CTQ2013-42532-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 1.261 2015 CHEMISTRY, INORGANIC & NUCLEAR 31 / 46 = 0.674 2015 Q3 T3 0.454 2015 Inorganic Chemistry 2015 Q3 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Álvarez-Vergara, M.C. (orcid)0000-0002-3327-0918 Pérez-Torrente, J.J. Universidad de Zaragoza (orcid)0000-0001-8054-2237 Lahoz, F.J. Universidad de Zaragoza Dobrinovich, I.T. (orcid)0000-0001-7154-7239 Oro, L.A. Universidad de Zaragoza 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 641, 12-13 (2015), 2115-2121 Z. anorg. allg. Chem. ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 0044-2313 544670 http://zaguan.unizar.es/record/60633/files/texto_completo.pdf Postprint 116328 http://zaguan.unizar.es/record/60633/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:60633 articulos driver 2021-01-21-11:17:02 ARTICLE