TY - JOUR
T1 - Transition-metal complexes of phenoxy-imine ligands modified with pendant imidazolium salts: Synthesis, characterisation and testing as ethylene polymerisation catalysts
AU - Houghton, Jennifer
AU - Simonovic, Stevan
AU - Whitwood, Adrian C.
AU - Douthwaite, Richard E.
AU - Carabineiro, Sonia A.
AU - Yuan, Jian-Chao
AU - Marques, Maria M.
AU - Gomes, Pedro T.
PY - 2008/2/15
Y1 - 2008/2/15
N2 - Reaction between 3-((1R,2R)-2-{[1-(3,5-di-tert-butyl-2-hydroxy-phenyl)-meth-(E)-ylidene]-amino}-cyclohexyl)-1- isopropyl-4-phenyl3H- imidazol-1-ium bromide (1a) or the derivative 3-((1R,2R)-2-{[ 1-(2-hydroxy-5-nitro-phenyl)-meth-( E)- ylidene]- amino}- cyclohexyl)1- isopropyl- 4-phenyl-3H-imidazol-1-ium bromide (1b) and metal halides MCl(x center dot)yTHF (M = Zr, x = 4, y = 2; M= V, x = y = 3; M = Cr, x = y = 3), in THF, at -78 degrees C gives the metal complexes of general formula [ MClx(kappa(2)-N, O-(OC6H2RR2)-R-1 C( H)= N-C6H10-Im) 2][Br](2) ( where M = Zr, x = 2, R-1= R-2 = Bu-t, 2; M = Zr, x = 2, R-1= H, R-2= NO2, 3; M= V, x = 1, R-1= R-2 = Bu-t, 4; M = Cr, x = 1, R-1= R-2 = Bu-t, 5; M = Fe, x = 0, R-1= R-2 = Bu-t, 6; Im = 1-isopropyl-4-phenyl-3H-imidazol-1-ium-3-yl). 1 H and C-13 NMR spectroscopy of 2 and 3 indicate kappa(2)- N, O-ligand coordination via the phenoxy-imine moiety with pendant imidazolium salt that is corroborated by a single crystal structure of 6. Compounds 2, 3, 4 and 5 were tested as precatalysts for ethylene polymerisation in the presence of methylaluminoxane (MAO) cocatalyst, showing low activity. Selected polymer samples were characterised by GPC showing multimodal molecular weight distributions. (c) 2007 Elsevier B. V. All rights reserved.
AB - Reaction between 3-((1R,2R)-2-{[1-(3,5-di-tert-butyl-2-hydroxy-phenyl)-meth-(E)-ylidene]-amino}-cyclohexyl)-1- isopropyl-4-phenyl3H- imidazol-1-ium bromide (1a) or the derivative 3-((1R,2R)-2-{[ 1-(2-hydroxy-5-nitro-phenyl)-meth-( E)- ylidene]- amino}- cyclohexyl)1- isopropyl- 4-phenyl-3H-imidazol-1-ium bromide (1b) and metal halides MCl(x center dot)yTHF (M = Zr, x = 4, y = 2; M= V, x = y = 3; M = Cr, x = y = 3), in THF, at -78 degrees C gives the metal complexes of general formula [ MClx(kappa(2)-N, O-(OC6H2RR2)-R-1 C( H)= N-C6H10-Im) 2][Br](2) ( where M = Zr, x = 2, R-1= R-2 = Bu-t, 2; M = Zr, x = 2, R-1= H, R-2= NO2, 3; M= V, x = 1, R-1= R-2 = Bu-t, 4; M = Cr, x = 1, R-1= R-2 = Bu-t, 5; M = Fe, x = 0, R-1= R-2 = Bu-t, 6; Im = 1-isopropyl-4-phenyl-3H-imidazol-1-ium-3-yl). 1 H and C-13 NMR spectroscopy of 2 and 3 indicate kappa(2)- N, O-ligand coordination via the phenoxy-imine moiety with pendant imidazolium salt that is corroborated by a single crystal structure of 6. Compounds 2, 3, 4 and 5 were tested as precatalysts for ethylene polymerisation in the presence of methylaluminoxane (MAO) cocatalyst, showing low activity. Selected polymer samples were characterised by GPC showing multimodal molecular weight distributions. (c) 2007 Elsevier B. V. All rights reserved.
KW - chromium
KW - iron
KW - zirconium
KW - phenoxy-imine ligands
KW - imidazolium salts
KW - ethylene polymerisation
KW - LIVING OLEFIN POLYMERIZATION
KW - SCHIFF-BASE LIGANDS
KW - TITANIUM COMPLEXES
KW - CHELATE LIGANDS
KW - FI CATALYSTS
KW - PROPYLENE POLYMERIZATION
KW - ZIRCONIUM COMPLEXES
KW - SALICYLALDIMINATO COMPLEXES
KW - ETHENE POLYMERIZATION
KW - BLOCK-COPOLYMERS
UR - http://www.scopus.com/inward/record.url?scp=38649134173&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2007.11.060
DO - 10.1016/j.jorganchem.2007.11.060
M3 - Article
SN - 0022-328X
VL - 693
SP - 717
EP - 724
JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY
JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY
IS - 4
ER -