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The synthesis, structure and ethene polymerisation catalysis of mono(salicylaldiminato) titanium and zirconium complexes

The synthesis, structure and ethene polymerisation catalysis of mono(salicylaldiminato) titanium and zirconium complexes
The synthesis, structure and ethene polymerisation catalysis of mono(salicylaldiminato) titanium and zirconium complexes
The silyl ethers 3- Bu-t - 2- ( OSiMe3) C6H3CH = NR ( 2a- e) have been prepared by deprotonation of the known iminophenols ( 1a - e) and treatment with SiClMe3 ( a, R = C6H5; b, R = 2,6- Pr-i 2C6H3; c, R = 2,4,6- Me3C6H2; d, R = 2- C6H5C6H4; e, R = C6F5). 2a - c react with TiCl4 in hydrocarbon solvents to give the binuclear complexes [ Ti {3- Bu-t - 2-( O) C6H3CH = N( R)} Cl( mu - Cl-3) TiCl3] ( 3a - c). The pentafluorophenyl species 2e reacts with TiCl4 to give the known complex Ti {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-2(2). The mononuclear five- coordinate complex, Ti {3- Bu-t - 2- ( O) C6H3CH = N( 2,4,6- Me3C6H2)} Cl-3 ( 4c), was isolated after repeated recrystallisation of 3c. Performing the dehalosilylation reaction in the presence of tetrahydrofuran yields the octahedral, mononuclear complexes Ti {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-3( THF) ( 5a - e). The reaction with ZrCl4( THF) (2) proceeds similarly to give complexes Zr {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-3( THF) ( 6b - e). The crystal structures of 3b, 4c, 5a, 5c, 5e, 6b, 6d, 6e and the salicylaldehyde titanium complex Ti {3- Bu-t - 2- ( O) C6H3CH = O} Cl-3( THF) ( 7) have been determined. Activation of complexes 5a e and 6b e with MAO in an ethene saturated toluene solution gives polyethylene with at best high activity depending on the imine substituent.
imine chelate ligands, phenoxy-imine, olefin polymerization, living polymerization, crystal-structure, benzyl complexes, ethylene, propylene, monocyclopentadienyl, hafnium
1477-9226
561-571
Pennington, Dale A.
0b00c86f-c4f9-4893-9e67-8311d755f990
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Harrington, Ross W.
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Hursthouse, Michael B.
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Hughes, David L.
d3b8245e-976a-47e6-8fe6-6ebcf38e2255
Light, Mark E.
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Schormann, Mark
5cd96b97-d850-44f3-8a3a-b1c1229ed624
Bochmann, Manfred
ec2bb201-23cc-4f91-aa80-258e6c8cc9fb
Lancaster, Simon J.
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Pennington, Dale A.
0b00c86f-c4f9-4893-9e67-8311d755f990
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Harrington, Ross W.
01d1f0bc-fc3e-43ae-a087-6cce0278128e
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Hughes, David L.
d3b8245e-976a-47e6-8fe6-6ebcf38e2255
Light, Mark E.
13b5eb33-3114-4fb7-8500-90ce69e9933c
Schormann, Mark
5cd96b97-d850-44f3-8a3a-b1c1229ed624
Bochmann, Manfred
ec2bb201-23cc-4f91-aa80-258e6c8cc9fb
Lancaster, Simon J.
06d860ba-99d7-4be1-a78d-39505c0fc14b

Pennington, Dale A., Clegg, William, Coles, Simon J., Harrington, Ross W., Hursthouse, Michael B., Hughes, David L., Light, Mark E., Schormann, Mark, Bochmann, Manfred and Lancaster, Simon J. (2005) The synthesis, structure and ethene polymerisation catalysis of mono(salicylaldiminato) titanium and zirconium complexes. Dalton Transactions, (3), 561-571. (doi:10.1039/b414229b).

Record type: Article

Abstract

The silyl ethers 3- Bu-t - 2- ( OSiMe3) C6H3CH = NR ( 2a- e) have been prepared by deprotonation of the known iminophenols ( 1a - e) and treatment with SiClMe3 ( a, R = C6H5; b, R = 2,6- Pr-i 2C6H3; c, R = 2,4,6- Me3C6H2; d, R = 2- C6H5C6H4; e, R = C6F5). 2a - c react with TiCl4 in hydrocarbon solvents to give the binuclear complexes [ Ti {3- Bu-t - 2-( O) C6H3CH = N( R)} Cl( mu - Cl-3) TiCl3] ( 3a - c). The pentafluorophenyl species 2e reacts with TiCl4 to give the known complex Ti {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-2(2). The mononuclear five- coordinate complex, Ti {3- Bu-t - 2- ( O) C6H3CH = N( 2,4,6- Me3C6H2)} Cl-3 ( 4c), was isolated after repeated recrystallisation of 3c. Performing the dehalosilylation reaction in the presence of tetrahydrofuran yields the octahedral, mononuclear complexes Ti {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-3( THF) ( 5a - e). The reaction with ZrCl4( THF) (2) proceeds similarly to give complexes Zr {3- Bu-t - 2- ( O) C6H3CH = N( R)} Cl-3( THF) ( 6b - e). The crystal structures of 3b, 4c, 5a, 5c, 5e, 6b, 6d, 6e and the salicylaldehyde titanium complex Ti {3- Bu-t - 2- ( O) C6H3CH = O} Cl-3( THF) ( 7) have been determined. Activation of complexes 5a e and 6b e with MAO in an ethene saturated toluene solution gives polyethylene with at best high activity depending on the imine substituent.

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Published date: 2005
Keywords: imine chelate ligands, phenoxy-imine, olefin polymerization, living polymerization, crystal-structure, benzyl complexes, ethylene, propylene, monocyclopentadienyl, hafnium

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Local EPrints ID: 20882
URI: http://eprints.soton.ac.uk/id/eprint/20882
ISSN: 1477-9226
PURE UUID: 50b5905e-2f81-4c83-8b25-5f8679b82211

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Date deposited: 02 Mar 2006
Last modified: 15 Jul 2019 19:25

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Contributors

Author: Dale A. Pennington
Author: William Clegg
Author: Simon J. Coles
Author: Ross W. Harrington
Author: Michael B. Hursthouse
Author: David L. Hughes
Author: Mark E. Light
Author: Mark Schormann
Author: Manfred Bochmann
Author: Simon J. Lancaster

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