doi:10.1002/zaac.201500566engCasado, M.A.Álvarez-Vergara, M.C.Pérez-Torrente, J.J.Lahoz, F.J.Dobrinovich, I.T.Oro, L.A.Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate LigandsART-2015-92241Treatment 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.2015http://zaguan.unizar.es/record/6063310.1002/zaac.201500566http://zaguan.unizar.es/record/60633oai:zaguan.unizar.es:60633info:eu-repo/grantAgreement/ES/DGA/E07info:eu-repo/grantAgreement/ES/DGA/E70info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2009-0050info:eu-repo/grantAgreement/ES/MINECO/CTQ2012–35665info:eu-repo/grantAgreement/ES/MINECO/CTQ2013-42532-PZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 641, 12-13 (2015), 2115-2121All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess