We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands.
- Authors
Casado, Miguel A.; Álvarez‐Vergara, M. Carmen; Pérez‐Torrente, Jesús J.; Lahoz, Fernando J.; Dobrinovich, Isabel T.; Oro, Luis A.
- Abstract
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 [Cp tt2ZrMe2] with protic ligands allowed directing the reactivity towards protonation of the methyl groups attached to zirconium. To check this approach we reacted [Cp tt2ZrMe2] with methanol affording complex [Cp tt2ZrMe(OMe)] ( 2), which was characterized in situ by NMR techniques. In the same line, the reaction of [Cp tt2ZrMe2] with 2-hydroxypyridine gave complex [Cp tt2Zr(Me)(Opy)] ( 3); forcing the conditions of this reaction did not lead to the expected complex [Cp tt2Zr(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 [Cp tt2ZrMe2] occurred, allowing the isolation of mononuclear complex [Cp tt2Zr(κ S,κ S,κ 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.
- Subjects
TITANIUM compounds synthesis; ZIRCONIUM compounds synthesis; LIGANDS (Chemistry); HYDROXYPYRIDINES; METALLOCENES
- Publication
Zeitschrift für Anorganische und Allgemeine Chemie, 2015, Vol 641, Issue 12/13, p2115
- ISSN
0044-2313
- Publication type
Article
- DOI
10.1002/zaac.201500566