RT info:eu-repo/semantics/article
T1 Zirconium and hafnium complexes with (allylsilyl)(η-amidosilyl)-η5-cyclopentadienyl ligands: synthesis, structure and reactivity
A1 Ramos Martín, Cristina
A1 Royo Gracia, Pascual
A1 Lanfranchi, Maurizio
A1 Pellinghelli, Maria Angela
A1 Tiripicchio, Antonio
K1 Insertion
K1 Isocyanides
K1 Hafnium
K1 Metallocenes
K1 Zirconium
K1 Ciencia
K1 Química inorgánica
K1 Science
K1 Chemistry, inorganic
AB The disubstituted cyclopentadiene C5H4(SiMe2Cl)[SiMe2(CH2CH=CH2)] was isolated by reaction of the lithium salt [Li{C5H4SiMe2(CH2CH=CH2)}] with SiMe2Cl2. It was then treated with NH2tBu and LiNH(2,6-Me2C6H3) to give the (aminosilyl)cyclopentadienes C5H4[SiMe2(CH2CH=CH2)][SiMe2(NHR)], which were further deprotonated to their dilithium salts [Li2{1-SiMe2NR-3-SiMe2(CH2CH=CH2)C5H3}] (R = tBu, 2,6-Me2C6H3). Reactions of the metal halides ZrCl4(THF)2 and HfCl4 with these dilithium salts, followed by alkylation of the resulting dichloro complexes, afforded the (η1-amidosilyl)-η5-cyclopentadienyl complexes [M{η5-C5H3(SiMe2-η1-NR)[SiMe2(CH2CH=CH2)]}X2] (R = tBu, 2,6-Me2C6H3; X = Cl, Me, CH2Ph; M = Zr, Hf). Only the bis(iminoacyl) complexes [M{η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}{η2-CR=N(2,6-Me2C6H3)}2] (M = Zr, Hf; R = Me, CH2Ph) could be isolated when the dialkylzirconium and -hafnium complexes were treated with CN(2,6-Me2C6H3); these were slowly transformed into the C–C-coupled diazametallacyclopentene compounds [M{η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}{η1-N(2,6-Me2C6H3)-CR=CR-η1-N(2,6-Me2C6H3)}] (R = Me, CH2Ph, M = Zr; R = Me, M = Hf) when their toluene solutions were heated to 70 °C–80 °C for long periods (2–4 d). The structural characterisation of all of the new compounds is described and the molecular structure of the dimeric dichlorozirconocene [ZrCl(μ-Cl){η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}]2, was determined by X-ray diffraction methods. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
PB John Wiley & Sons
SN 1099-0682
YR 2005
FD 2005
LK http://hdl.handle.net/10017/4182
UL http://hdl.handle.net/10017/4182
LA eng
DS MINDS@UW
RD 02-may-2024