Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations

Lewis M. Broomfield; Yann Sarazin; Joseph A. Wright; David L. Hughes; William Clegg; Ross W. Harrington; Manfred Bochmann

doi:10.1016/j.jorganchem.2007.04.047

Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations

Lewis M. Broomfield, Yann Sarazin, Joseph A. Wright, David L. Hughes, William Clegg, Ross W. Harrington, Manfred Bochmann

Research output: Contribution to journal › Article › peer-review

21 Citations (Scopus)

Abstract

Treatment of MCl₃(OC₆H₃-2-^tBu-6-CH==NC₆F₅)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K⁺[RN==CHC₄H₃N]^-), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl₂(N–O)(N–N). The molecular structures of TiCl₂(OC₆H₃-2-^tBu-6-CH==NC₆F₅)(C₂H₅N==CHC₄H₃N) (1c), TiCl₂(OC₆H₃-2-^tBu-6-CH==NC₆F₅)(C₆H₁₁N==CHC₄H₃N) (1b) and ZrCl₂(OC₆H₃-2-^tBu-6-CH==NC₆F₅)(C₆H₁₁N==CHC₄H₃N) (2b) show distorted octahedral geometries with trans-O^-,N^-/cis-Cl₂ arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene–propylene copolymers show ca. 80% 1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure.

Original language	English
Pages (from-to)	4603-4611
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	692
Issue number	21
DOIs	https://doi.org/10.1016/j.jorganchem.2007.04.047
Publication status	Published - 10 May 2007

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10.1016/j.jorganchem.2007.04.047

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@article{0d512985c37345b5900971c5dafe399b,

title = "Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations",

abstract = "Treatment of MCl3(OC6H3-2-tBu-6-CH==NC6F5)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K+[RN==CHC4H3N]-), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl2(N–O)(N–N). The molecular structures of TiCl2(OC6H3-2-tBu-6-CH==NC6F5)(C2H5N==CHC4H3N) (1c), TiCl2(OC6H3-2-tBu-6-CH==NC6F5)(C6H11N==CHC4H3N) (1b) and ZrCl2(OC6H3-2-tBu-6-CH==NC6F5)(C6H11N==CHC4H3N) (2b) show distorted octahedral geometries with trans-O-,N-/cis-Cl2 arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene–propylene copolymers show ca. 80% 1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure.",

author = "Broomfield, {Lewis M.} and Yann Sarazin and Wright, {Joseph A.} and Hughes, {David L.} and William Clegg and Harrington, {Ross W.} and Manfred Bochmann",

year = "2007",

month = may,

day = "10",

doi = "10.1016/j.jorganchem.2007.04.047",

language = "English",

volume = "692",

pages = "4603--4611",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "21",

}

Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations. / Broomfield, Lewis M.; Sarazin, Yann; Wright, Joseph A.; Hughes, David L.; Clegg, William; Harrington, Ross W.; Bochmann, Manfred.

In: Journal of Organometallic Chemistry, Vol. 692, No. 21, 10.05.2007, p. 4603-4611.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations

AU - Broomfield, Lewis M.

AU - Sarazin, Yann

AU - Wright, Joseph A.

AU - Hughes, David L.

AU - Clegg, William

AU - Harrington, Ross W.

AU - Bochmann, Manfred

PY - 2007/5/10

Y1 - 2007/5/10

N2 - Treatment of MCl3(OC6H3-2-tBu-6-CH==NC6F5)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K+[RN==CHC4H3N]-), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl2(N–O)(N–N). The molecular structures of TiCl2(OC6H3-2-tBu-6-CH==NC6F5)(C2H5N==CHC4H3N) (1c), TiCl2(OC6H3-2-tBu-6-CH==NC6F5)(C6H11N==CHC4H3N) (1b) and ZrCl2(OC6H3-2-tBu-6-CH==NC6F5)(C6H11N==CHC4H3N) (2b) show distorted octahedral geometries with trans-O-,N-/cis-Cl2 arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene–propylene copolymers show ca. 80% 1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure.

AB - Treatment of MCl3(OC6H3-2-tBu-6-CH==NC6F5)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K+[RN==CHC4H3N]-), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl2(N–O)(N–N). The molecular structures of TiCl2(OC6H3-2-tBu-6-CH==NC6F5)(C2H5N==CHC4H3N) (1c), TiCl2(OC6H3-2-tBu-6-CH==NC6F5)(C6H11N==CHC4H3N) (1b) and ZrCl2(OC6H3-2-tBu-6-CH==NC6F5)(C6H11N==CHC4H3N) (2b) show distorted octahedral geometries with trans-O-,N-/cis-Cl2 arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene–propylene copolymers show ca. 80% 1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure.

U2 - 10.1016/j.jorganchem.2007.04.047

DO - 10.1016/j.jorganchem.2007.04.047

M3 - Article

VL - 692

SP - 4603

EP - 4611

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 21

ER -