Neutral and Cationic [Bis(η1-amidosilyl)-η5-cyclopentadienyl]titanium and -zirconium complexes: synthesis, X-ray molecular structures and DFT calculations
Autores
Cano Sierra, Jesús; Royo Gracia, Pascual; Jacobsen, Heiko; Blacque, Olivier; Berke, Heinz; [et al.]Identificadores
Enlace permanente (URI): http://hdl.handle.net/10017/4188DOI: 10.1002/ejic.200200698
ISSN: 1434-1948
Editor
John Wiley & Sons
Fecha de publicación
2003Patrocinadores
The authors acknowledge the MCyT (project MAT2001-1309) for
financial support and the EC (project COST-D12/0016/98). J. C.
acknowledges CAM for a fellowship.
Cita bibliográfica
European Journal of Inorganic Chemistry, 2003, 2463-2474
Palabras clave
Cations
Cyclopentadienyl ligands
Density functional calculations
Nitrogen ligands
Titanium
Zirconium
Proyectos
MAT2001-1309 (Ministerio de Ciencia y Tecnología)
info:eu-repo/COST-D12/0016/98
Tipo de documento
info:eu-repo/semantics/article
Versión
info:eu-repo/semantics/publishedVersion
Versión del editor
http://dx.doi.org/10.1002/ejic.200200698Derechos
(c) Wiley, 2003
Derechos de acceso
info:eu-repo/semantics/openAccess
Resumen
Treatment of LiNHtBu with THF solutions of C5H4(SiMe2Cl)2 gave C5H4(SiMe2NHtBu)2 (1). Deprotonation of 1 with M(NMe2)4 (M = Ti, Zr) under different conditions provided the monocyclopentadienyl complexes [M{η5-C5H3- [SiMe2(NHtBu)]2}(NMe2)3] [M = Ti (2), Zr (3)] and the single (η-amidosilyl)cyclopentadienyl compounds [M{η5-C5H3[SiMe2(NHtBu)][SiMe2(η1-NtBu)]}(NMe2)2] [M = Ti (4), Zr (5)]. The related dibenzyl compounds [M{η5-C5H3[SiMe2- (NHtBu)][SiMe2(η1-NtBu)]}(CH2Ph)2] [M = Ti (6), Zr (7)] resulted from treatment of 1 with M(CH2C6H5)4 (M = Ti, Zr). Further deprotonation of the amido complexes 4 and 5 and the benzyl complexes 6 and 7 by heating in toluene solution gave the bis(η-amidosilyl)cyclopentadienyl complexes [M{η5-C5H3[SiMe2(η1-NtBu)]2}(NMe2)] [M = Ti (8), Zr (9)] and [M{η5-C5H3[SiMe2(η1-NtBu)]2}(CH2Ph)] [M = Ti (10), Zr (11)], respectively. Treatment of the monobenzyl complexes 10 and 11 with B(C6F5)3 yielded the cationic compounds [M{η5-C5H3[SiMe2(η1-NtBu)]2}]+ as [(CH2Ph)B(C6F5)3] − [M = Ti (12), Zr (13)] salts. All new compounds were characterized by NMR spectroscopy, and the crystal structures of 10 and 13 were studied by diffraction methods. DFT calculations for the neutral and cationic species are described and provide an explanation for the unusual η1 coordination of a phenyl ring to a group-4 metal cation
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