Resumen: 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. Idioma: Inglés DOI: 10.1002/zaac.201500566 Año: 2015 Publicado en: ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 641, 12-13 (2015), 2115-2121 ISSN: 0044-2313 Factor impacto JCR: 1.261 (2015) Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 31 / 46 = 0.674 (2015) - Q3 - T3 Factor impacto SCIMAGO: 0.454 - Inorganic Chemistry (Q3)