Chiral complexes of a new diazaallyl ligand: Group 4 aminooxazolinates
UNSPECIFIED (2004) Chiral complexes of a new diazaallyl ligand: Group 4 aminooxazolinates. ORGANOMETALLICS, 23 (21). pp. 5066-5074. ISSN 0276-7333Full text not available from this repository.
Official URL: http://dx.doi.org/10.1021/om049518s
A new biaryl-bridged bis(iminooxazolidine) proligand H2L is prepared in good yield from 2,2-diamino-6,6'-dimethylbiphenyl. The direct reaction of H2L with [Ti(CH2Ph)(4)] leads via deprotonation of the ligand to the C-2-symmetric dibenzyl complex [LTi(CH2Ph)(2)] (85%) containing diazaallyl ligation. The analogous group 4 complexes [LZr(CH2Ph)(2)] (79%) and [LHf(CH2Ph)(2)] (91%) are similarly obtained. Molecular structures of these three compounds indicate C-2-symmetry in all cases and that the chirality of the backbone is well expressed in the coordination sphere. Reaction of H2L with Ti(NMe2)(4) gives the amide [LTi(NMe2)(2)] (90%), which on reaction with SiMe3Cl gives the chloride [LTiCl2] (78%). The dichloride [LZr(NMe2H)Cl-2] is prepared via treatment of H2L with Zr(NMe2)(2)Cl-2(THF)(2) (86%). The direct reaction of H2L with TiCl4(THF)(2) gives the adduct [(H2L)TiCl4] (83%), which is shown by X-ray crystallography to contain intramolecular (NHCl)-Cl-... hydrogen bond contacts. The complexes were tested as precatalysts for the polymerization of ethene and 1-hexene using a range of cocatalysts and were found to display low activity. Correspondingly, NMR studies on a presumed active species [LZr(CH2Ph)] [B(C6F5)(3)(CH2Ph)] were consistent with tight ion pairing on the NMR chemical shift time scale.
|Item Type:||Journal Item|
|Subjects:||Q Science > QD Chemistry|
|Journal or Publication Title:||ORGANOMETALLICS|
|Publisher:||AMER CHEMICAL SOC|
|Date:||11 October 2004|
|Number of Pages:||9|
|Page Range:||pp. 5066-5074|
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