Imperial College London
Professor Vernon C. Gibson, FRS

Professor Vernon C. Gibson, FRS

Faculty of Engineering, Department of Materials

Visiting Professor
 
 
 
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Contact

 

+44 (0)20 7594 2783v.gibson

 
 
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Location

 

2.27Bessemer BuildingSouth Kensington Campus

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Summary

 

Publications

Citation

BibTex format

@article{Cariou:2009:10.1016/j.jorganchem.2008.11.064,
author = {Cariou, R and Gibson, VC and Tomov, AK and White, AJP},
doi = {10.1016/j.jorganchem.2008.11.064},
journal = {J. Organomet. Chem.},
pages = {703--716},
title = {Group 4 metal complexes bearing new tridentate (NNO) ligands: Benzyl migration and formation of unusual C-C coupled products.},
url = {http://dx.doi.org/10.1016/j.jorganchem.2008.11.064},
volume = {694},
year = {2009}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - Group 4 metal complexes bearing new phenoxy(benzimidazolyl)-imine, -amine and -amide ligands have been synthesized.  A series of metal chloride derivs. has been prepd. via treatment of MCl4(THF)2 (M = Ti, Zr, Hf) with the in situ generated sodium salt of the (benzimidazolyl)imine phenol 1.  Reaction of the pro-ligand 2 with TiCl4(THF)2 afforded the corresponding complex 8 in which the amine proton remains bound to the nitrogen donor.  Benzyl complexes of zirconium and hafnium were synthesized via treatment of pro-ligands 1 and 2 with M(CH2Ph)4 precursors.  The complexes [NNO]M(CH2Ph)3 (6 M = Zr, 7 M = Hf) were found to undergo benzyl migration from the metal center to the imine carbon of the ligand backbone giving complexes 11 and 12; the migration follows first order kinetics.  The reaction of 1 with Ti(NMe2)4 led to the formation of an unusual C-C coupled product in which a new piperazine ring has formed.  Complexes 11 and 12 undergo related transformations, leading to analogous C-C coupled products which were characterized by x-ray crystallog.  Deuterium labeling expts. were carried out to det. the mechanistic pathway of the reactions.  Chloride and benzyl complexes 3-12 were screened as pre-catalysts for olefin polymn. [on SciFinder(R)]
AU  - Cariou,R
AU  - Gibson,VC
AU  - Tomov,AK
AU  - White,AJP
DO  - 10.1016/j.jorganchem.2008.11.064
EP  - 716
PY  - 2009///
SN  - 0022-328X
SP  - 703
TI  - Group 4 metal complexes bearing new tridentate (NNO) ligands: Benzyl migration and formation of unusual C-C coupled products.
T2  - J. Organomet. Chem.
UR  - http://dx.doi.org/10.1016/j.jorganchem.2008.11.064
VL  - 694
ER  -
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