0000000000274196
AUTHOR
Karen E. Du Plooy
Alkyl Complexes of Group 4 Metals Containing a Tridentate-Linked Amido−Cyclopentadienyl Ligand: Synthesis, Structure, and Reactivity Including Ethylene Polymerization Catalysis
A series of group 4 metal complexes M(η5:η1:η1-C5Me4SiMe2NCH2CH2X)R2 (M = Ti; R = Me, CH2Ph; M = Zr, Hf; R = Me, Et, nPr, nBu, CH2Ph, CH2SiMe3, Ph) containing the tridentate-linked amido−tetramethy...
Zirconium, hafnium and yttrium complexes containing two linked amido— tetramethylcyclopentadienyl ligands: Synthesis, reactivity and molecular structure of Hf(η5:η1−C5Me4SiMe2NiPr)2
Abstract Zirconium and hafnium complexes M(η5: η1−C5Me4SiMe2NR′)xCl(4−2x) (M = Zr, Hf; x = 1, 2; R′ = iPr, tBu) containing one or two linked amido-tetramethylcyclopentadienyl ligands C5Me4SiMe2NR′ have been synthesized by the reaction of the dilithium derivative Li2(C5Me4SiMe2NR′) with MCl4(THF)2. The crystal structure of the hafnium complex Hf(η5: η1−C5Me4SiMe2NiPr)2 has been determined by a single-crystal X-ray diffraction study and shows a C2-symmetric helical metallocene, in which the amido ligands are bonded as π-donor ligands with Hf—N bond lengths of 2.115(2) A. The isoelectronic heterobimetallic yttrium complex Li[Y(η5: η1−C5Me4SiMe2NCH2CH2OMe)2] reacts with phenylacetylene to give …
Zirconium and hafnium mono(alkyl) complexes containing a tridentate linked amido-tetramethylcyclopentadienyl ligand. Molecular structure of Hf(η5:η1:η1-C5Me4SiMe2NCH2CH2OCH3)Cl2
Abstract Zirconium and hafnium complexes M( η 5 : η 1 : η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe)Cl 2 (M=Zr, Hf) containing the tridentate 2-methoxyethylamido-functionalized tetramethylcyclopentadienyl ligand C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe have been synthesized by the reaction of the dilithium derivative Li 2 [C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe] with MCl 4 (THF) 2 . Selective monoalkylation of the dichloro complexes gave complexes of the type M( η 5 : η 1 : η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe)(R)Cl (R=CH 2 Ph, o -C 6 H 4 CH 2 NMe 2 ). The crystal structure of the hafnium dichloro complex Hf( η 5 : η 1 : η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe)Cl 2 has been determined by X-ray crystal diffraction and sho…