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Novel amido/imino, diamido/ether and phenoxyimine early transition metal complexes

Novel amido/imino, diamido/ether and phenoxyimine early transition metal complexes
Novel amido/imino, diamido/ether and phenoxyimine early transition metal complexes

A series of novel, mixed donor amino/imino ligands have been synthesised in high yield and converted to the corresponding lithium amido/imino compounds. Both the amino/imino and the lithium amido/imino compounds were reacted with Group 4 metal complexes to give amido/imino and related complexes of Ti and Zr. Early transition metal complexes of a phenoxyimine ligand were prepared using both aminolysis and salt elimination methodologies. A series of novel diamido-ether ligands were prepared based on a xanthene or dibenzofuran framework, and several Ti complexes were prepared.

The silylamino/imino compounds 2-[CyN=C(CH3)]C6H4N(H)(SiMe3)(LTMSH) and 2-[CyN=C(CH3)]C6H4N(H)(SiMe2But)(LTBDMSH) were synthesised in high yields by reaction of 2-[CyN=C(CH3)]C6H4N(H)Li with Me3SiC1 and ButMe2SiC1 respectively. The arylamino/imino compounds 2-[CyN=C(CH3)]C6H4N(H)(xyl) (LxylH) and 2-[CyN=C(CH3)]C6H4N(H)(mes) (LmesH) were prepared in high yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH3)]C6H4NH2. The amino/imino ligands were deprotonated with BunLi to yield the respective lithium amido/imino complexes (LLi).

University of Southampton
Porter, Robin Mark
9c5ffe31-179b-407f-a9d3-70bc6bff4780
Porter, Robin Mark
9c5ffe31-179b-407f-a9d3-70bc6bff4780

Porter, Robin Mark (2004) Novel amido/imino, diamido/ether and phenoxyimine early transition metal complexes. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

A series of novel, mixed donor amino/imino ligands have been synthesised in high yield and converted to the corresponding lithium amido/imino compounds. Both the amino/imino and the lithium amido/imino compounds were reacted with Group 4 metal complexes to give amido/imino and related complexes of Ti and Zr. Early transition metal complexes of a phenoxyimine ligand were prepared using both aminolysis and salt elimination methodologies. A series of novel diamido-ether ligands were prepared based on a xanthene or dibenzofuran framework, and several Ti complexes were prepared.

The silylamino/imino compounds 2-[CyN=C(CH3)]C6H4N(H)(SiMe3)(LTMSH) and 2-[CyN=C(CH3)]C6H4N(H)(SiMe2But)(LTBDMSH) were synthesised in high yields by reaction of 2-[CyN=C(CH3)]C6H4N(H)Li with Me3SiC1 and ButMe2SiC1 respectively. The arylamino/imino compounds 2-[CyN=C(CH3)]C6H4N(H)(xyl) (LxylH) and 2-[CyN=C(CH3)]C6H4N(H)(mes) (LmesH) were prepared in high yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH3)]C6H4NH2. The amino/imino ligands were deprotonated with BunLi to yield the respective lithium amido/imino complexes (LLi).

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Published date: 2004

Identifiers

Local EPrints ID: 465414
URI: http://eprints.soton.ac.uk/id/eprint/465414
PURE UUID: c87e0da6-b0b7-4be4-a824-39870406701a

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Date deposited: 05 Jul 2022 00:49
Last modified: 16 Mar 2024 20:09

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Author: Robin Mark Porter

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