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(Alkyliminomethyl)phenylamido and related complexes of zirconium and titanium

(Alkyliminomethyl)phenylamido and related complexes of zirconium and titanium
(Alkyliminomethyl)phenylamido and related complexes of zirconium and titanium
A range of trialkylsilylamido complexes of zirconium in which the silylamido functional group is attached to an o-(alkyliminomethyl)- or an o-(alkyliminoethyl)-substituted aromatic ring have been synthesised by salt elimination or aminolysis reactions and characterised by spectroscopic and diffraction methods. The monoanionic ligands (L), formally isoelectronic to the cyclopentadienyl ligand, can be introduced to zirconium by reaction of LLi with ZrCl4 under a variety of conditions giving rise to complexes of type LZrCl3 and L2ZrCl2, by reaction of LLi with Zr(NMe2)(2)Cl-2 (THF)(2), and Zr(NEt2)(2) Cl-2 (THF)(2) giving rise to LZrCl(NMe2)(2)Cl and LZrCl(NEt2)(2)Cl, respectively, or by reaction of LH with Zr(NMe2)(4) giving rise to LZr(NMe2)(3). LZr(NMe2)(2)Cl and LZr(NEt2)(2)Cl can be transformed to LZrCl3 by reaction with Me3SiCl, while LZr(NMe2)(3) on heating rearranges to dimeric imido complexes by elimination of amidosilanes. Aminolysis of Zr(NMe2)(2)Cl-2 (THF)(2) with LH results in a formal insertion of the imino C=N into the Zr-amido bond. The combination of enolisable imine and a bulky silyl amide gave rise to a new mixed donor ligand system comprising of one silylamido and one eneamido group. Finally aminolysis of Ti(NMe2)Cl-2 with LH resulted in the isolation of a C-3 symmetric triamido titanium complex.
diketiminate ligands, ethylene, polymerization, catalysts, chemistry, 5-coordinate, derivatives, lithium
1477-9226
3290-3299
Porter, Robin M.
0f562df9-d217-4c62-a3c5-66b67262dcfb
Winston, Scott
d7cc4b37-c1c0-4c11-b210-c172d21fc544
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Porter, Robin M.
0f562df9-d217-4c62-a3c5-66b67262dcfb
Winston, Scott
d7cc4b37-c1c0-4c11-b210-c172d21fc544
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Porter, Robin M., Winston, Scott, Danopoulos, Andreas A. and Hursthouse, Michael B. (2002) (Alkyliminomethyl)phenylamido and related complexes of zirconium and titanium. Dalton Transactions, (17), 3290-3299. (doi:10.1039/b202471c).

Record type: Article

Abstract

A range of trialkylsilylamido complexes of zirconium in which the silylamido functional group is attached to an o-(alkyliminomethyl)- or an o-(alkyliminoethyl)-substituted aromatic ring have been synthesised by salt elimination or aminolysis reactions and characterised by spectroscopic and diffraction methods. The monoanionic ligands (L), formally isoelectronic to the cyclopentadienyl ligand, can be introduced to zirconium by reaction of LLi with ZrCl4 under a variety of conditions giving rise to complexes of type LZrCl3 and L2ZrCl2, by reaction of LLi with Zr(NMe2)(2)Cl-2 (THF)(2), and Zr(NEt2)(2) Cl-2 (THF)(2) giving rise to LZrCl(NMe2)(2)Cl and LZrCl(NEt2)(2)Cl, respectively, or by reaction of LH with Zr(NMe2)(4) giving rise to LZr(NMe2)(3). LZr(NMe2)(2)Cl and LZr(NEt2)(2)Cl can be transformed to LZrCl3 by reaction with Me3SiCl, while LZr(NMe2)(3) on heating rearranges to dimeric imido complexes by elimination of amidosilanes. Aminolysis of Zr(NMe2)(2)Cl-2 (THF)(2) with LH results in a formal insertion of the imino C=N into the Zr-amido bond. The combination of enolisable imine and a bulky silyl amide gave rise to a new mixed donor ligand system comprising of one silylamido and one eneamido group. Finally aminolysis of Ti(NMe2)Cl-2 with LH resulted in the isolation of a C-3 symmetric triamido titanium complex.

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Published date: 2002
Keywords: diketiminate ligands, ethylene, polymerization, catalysts, chemistry, 5-coordinate, derivatives, lithium

Identifiers

Local EPrints ID: 19837
URI: http://eprints.soton.ac.uk/id/eprint/19837
ISSN: 1477-9226
PURE UUID: 93f78a19-f336-4026-ac17-aa6312c1f7b4

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Date deposited: 22 Feb 2006
Last modified: 08 Jan 2022 12:50

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Contributors

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

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