RT info:eu-repo/semantics/article
T1 Neutral and Cationic [Bis(η1-amidosilyl)-η5-cyclopentadienyl]titanium and -zirconium complexes: synthesis, X-ray molecular structures and DFT calculations
A1 Cano Sierra, Jesús
A1 Royo Gracia, Pascual
A1 Jacobsen, Heiko
A1 Blacque, Olivier
A1 Berke, Heinz
A1 Herdtweck, Eberhardt
K1 Cations
K1 Cyclopentadienyl ligands
K1 Density functional calculations
K1 Nitrogen ligands
K1 Titanium
K1 Zirconium
K1 Ciencia
K1 Química inorgánica
K1 Science
K1 Chemistry, inorganic
AB 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
PB John Wiley & Sons
SN 1434-1948
YR 2003
FD 2003
LK http://hdl.handle.net/10017/4188
UL http://hdl.handle.net/10017/4188
LA eng
NO The authors acknowledge the MCyT (project MAT2001-1309) forfinancial support and the EC (project COST-D12/0016/98). J. C.acknowledges CAM for a fellowship.
DS MINDS@UW
RD 25-abr-2024