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o-(Cyclohexyliminoethyl)(arylamido)benzene and related complexes of zirconium and titanium. The non-innocence of the ketimino functionality

o-(Cyclohexyliminoethyl)(arylamido)benzene and related complexes of zirconium and titanium. The non-innocence of the ketimino functionality
o-(Cyclohexyliminoethyl)(arylamido)benzene and related complexes of zirconium and titanium. The non-innocence of the ketimino functionality
N-Arylamido complexes of zirconium in which the amido functional group is attached to an o-(alkyliminoethyl) substituted aromatic ring, have been synthesised by salt elimination reactions and characterised by spectroscopic and diffraction methods; they are analogous to the N-silylamido species recently reported (Dalton Trans., 2002, 3290-3299). The ligands2-[CyN=C(CH3)]C6H4N(H)(xyl), (LH)-H-xyl, and 2-[CyN=C(CH3)] C6H4N(H)(mes) (LH)-H-mes, Cy = C6H11, xyl = 3,5-Me2C6H3 mes = 2,4,6-Me3C6H2, were prepared in good yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH3)]C6H4NH2. Reaction of (LLi)-Li-mes with Zr(NEt2)(2)Cl-2(thf)(2) gave after chloride substitution the arylamido ketimino complex (LZr)-Zr-mes(NEt2)(2)Cl 1; variable amounts of the arylamido vinylamido complex 2 were also obtained. Interaction of (LLi)-Li-mes or (LLi)-Li-xyl with Ti(NMe2)(2)Cl-2 gave rise to the tripodal bis-amido amino complexes 5 and 6 possibly formed by ligand rearrangement involving migration of the dimethylamido group to the ketimino carbon.
olefin polymerization, ligands, amination, catalysts, family
1477-9226
2556-2562
Porter, Robin M.
0f562df9-d217-4c62-a3c5-66b67262dcfb
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236
Porter, Robin M.
0f562df9-d217-4c62-a3c5-66b67262dcfb
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236

Porter, Robin M. and Danopoulos, Andreas A. (2004) o-(Cyclohexyliminoethyl)(arylamido)benzene and related complexes of zirconium and titanium. The non-innocence of the ketimino functionality. Dalton Transactions, (16), 2556-2562. (doi:10.1039/B404173A).

Record type: Article

Abstract

N-Arylamido complexes of zirconium in which the amido functional group is attached to an o-(alkyliminoethyl) substituted aromatic ring, have been synthesised by salt elimination reactions and characterised by spectroscopic and diffraction methods; they are analogous to the N-silylamido species recently reported (Dalton Trans., 2002, 3290-3299). The ligands2-[CyN=C(CH3)]C6H4N(H)(xyl), (LH)-H-xyl, and 2-[CyN=C(CH3)] C6H4N(H)(mes) (LH)-H-mes, Cy = C6H11, xyl = 3,5-Me2C6H3 mes = 2,4,6-Me3C6H2, were prepared in good yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH3)]C6H4NH2. Reaction of (LLi)-Li-mes with Zr(NEt2)(2)Cl-2(thf)(2) gave after chloride substitution the arylamido ketimino complex (LZr)-Zr-mes(NEt2)(2)Cl 1; variable amounts of the arylamido vinylamido complex 2 were also obtained. Interaction of (LLi)-Li-mes or (LLi)-Li-xyl with Ti(NMe2)(2)Cl-2 gave rise to the tripodal bis-amido amino complexes 5 and 6 possibly formed by ligand rearrangement involving migration of the dimethylamido group to the ketimino carbon.

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Published date: 2004
Keywords: olefin polymerization, ligands, amination, catalysts, family

Identifiers

Local EPrints ID: 20308
URI: http://eprints.soton.ac.uk/id/eprint/20308
ISSN: 1477-9226
PURE UUID: 761ba3ec-7933-4b72-a5b8-fc9b97086223

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Date deposited: 17 Feb 2006
Last modified: 15 Mar 2024 06:23

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Author: Robin M. Porter
Author: Andreas A. Danopoulos

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