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• W2114852908 abstract "Abstract The disubstituted cyclopentadiene C 5 H 4 (SiMe 2 Cl)[SiMe 2 (CH 2 CH=CH 2 )] was isolated by reaction of the lithium salt [Li{C 5 H 4 SiMe 2 (CH 2 CH=CH 2 )}] with SiMe 2 Cl 2 . It was then treated with NH 2 t Bu and LiNH(2,6‐Me 2 C 6 H 3 ) to give the (aminosilyl)cyclopentadienes C 5 H 4 [SiMe 2 (CH 2 CH=CH 2 )][SiMe 2 (NHR)], which were further deprotonated to their dilithium salts [Li 2 {1‐SiMe 2 NR‐3‐SiMe 2 (CH 2 CH=CH 2 )C 5 H 3 }] (R = t Bu, 2,6‐Me 2 C 6 H 3 ). Reactions of the metal halides ZrCl 4 (THF) 2 and HfCl 4 with these dilithium salts, followed by alkylation of the resulting dichloro complexes, afforded the (η 1 ‐amidosilyl)‐η 5 ‐cyclopentadienyl complexes [M{η 5 ‐C 5 H 3 (SiMe 2 ‐η 1 ‐NR)[SiMe 2 (CH 2 CH=CH 2 )]}X 2 ] (R = t Bu, 2,6‐Me 2 C 6 H 3 ; X = Cl, Me, CH 2 Ph; M = Zr, Hf). Only the bis(iminoacyl) complexes [M{η 5 ‐C 5 H 3 (SiMe 2 ‐η 1 ‐N t Bu)[SiMe 2 (CH 2 CH=CH 2 )]}{η 2 ‐CR=N(2,6‐Me 2 C 6 H 3 )} 2 ] (M = Zr, Hf; R = Me, CH 2 Ph) could be isolated when the dialkylzirconium and ‐hafnium complexes were treated with CN(2,6‐Me 2 C 6 H 3 ); these were slowly transformed into the C–C‐coupled diazametallacyclopentene compounds [M{η 5 ‐C 5 H 3 (SiMe 2 ‐η 1 ‐N t Bu)[SiMe 2 (CH 2 CH=CH 2 )]}{η 1 ‐N(2,6‐Me 2 C 6 H 3 )‐CR=CR‐η 1 ‐N(2,6‐Me 2 C 6 H 3 )}] (R = Me, CH 2 Ph, 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){η 5 ‐C 5 H 3 (SiMe 2 ‐η 1 ‐N t Bu)[SiMe 2 (CH 2 CH=CH 2 )]}] 2 , was determined by X‐ray diffraction methods. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)" @default.
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• W2114852908 date "2005-09-22" @default.
• W2114852908 modified "2023-10-18" @default.
• W2114852908 title "Zirconium and Hafnium Complexes with (Allylsilyl)(η‐amidosilyl)‐η⁵‐cyclopentadienyl Ligands: Synthesis, Structure and Reactivity" @default.
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• W2114852908 doi "https://doi.org/10.1002/ejic.200500379" @default.
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