Regioselective formation of [2-(η5-cyclopentadienyl)-2-fluorenylpropane]-titanium complexes: precursors, synthesis, structure and reactivity
Authors
Dorado Moreno, IvánIdentifiers
Permanent link (URI): http://hdl.handle.net/10017/4277DOI: 10.1016/S0022-328X(98)00576-2
ISSN: 0022-328X
Publisher
Elsevier
Date
1998Bibliographic citation
Journal of Organometallic Chemistry, 1998, v.563 n.1-2, p.7-14
Keywords
Bridged ligands
Cyclopentadienyl
Fluorenyl
Titanium complexes
Project
PB-92-0178-C (Ministerio de Educación y Cultura)
U.A. 012/96 (Universidad de Alcalá)
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Publisher's version
http://dx.doi.org/10.1016/S0022-328X(98)00576-2Rights
© Elsevier, 1998
Access rights
info:eu-repo/semantics/openAccess
Abstract
The 2-cyclopentadienyl-2-fluorenylpropane ligand has been converted into the monometalated derivatives M[CMe2(C5H4)(C13H9)] (M=Li, Tl,) and CMe2[C5H4(SiMe3)](C13H9). These alkylating reagents have been characterized, and used to synthesize a new series of organotitanium (IV) complexes. The trimethylsilyl derivative was treated with TiCl4 to give the monocyclopentadienyl compound [Ti{CMe2(η5-C5H4)(C13H9)}Cl3]. Reaction of the thallium derivative with [Ti(η5-C5R5)Cl3] afforded the ‘mixed-ring’ dicyclopentadienyl complexes [Ti{CMe2(η5-C5H4)(C13H9)}(η5-C5R5)Cl2] (R=H, Me), whereas the reaction of TiCl4 with two equivalents of the lithium compound led to the dicyclopentadienyl complex [Ti{CMe2(η5-C5H4)(C13H9)}2Cl2]. The monocyclopentadienyl compound [Ti{CMe2(η5-C5H4)(C13H9)}Cl3] was readily hydrolyzed to give [Ti{CMe2(η5-C5H4)(C13H9)}Cl2]2(μ-O) in wet acetone (0.5% H2O). The dicyclopentadienyl derivative [Ti{CMe2(η5-C5H4)(C13H9)}(η5-C5Me5)Cl2] was further converted into [Ti{CMe2(η5-C5H4)(C13H9)}(η5-C5Me5)Me2] by alkylation with LiMe. Structural data of the titanium complexes demonstrate the η5-coordination of the cyclopentadienyl ring of the ancillary ligand, whereas the fluorenyl ring is not coordinated to the metal center. This mode of coordination is confirmed by the X-ray crystal structure analysis of [Ti{CMe2(η5-C5H4)(C13H9)}2Cl2].
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