Oxide-Bridged Heterobimetallic Aluminum/Zirconium Catalysts for Ethylene Polymerization

Cedric Boulho; Harmen S. Zijlstra; Sjoerd Harder

doi:10.1002/ejic.201500123

Oxide-Bridged Heterobimetallic Aluminum/Zirconium Catalysts for Ethylene Polymerization

Cedric Boulho, Harmen S. Zijlstra, Sjoerd Harder^*

^*Corresponding author for this work

Molecular Inorganic Chemistry

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

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Abstract

A bimetallic aluminum/zirconium complex Cp*Zr-2(Me)OAl(DIPH) [DIPH-H-2 = 3,3-bis(2-methylallyl)-(1,1-biphenyl)-2,2-diol; Cp* = C5Me5] was prepared in good yield by the reaction of (DIPH)AlMe with Cp*Zr-2(Me)OH. In contrast to Roesky's catalyst, Cp2Zr(Me)O(Me)Al(DIPP-nacnac) {DIPP-nacnac = CH[(CMe)(2,6-iPr(2)C(6)H(3)N)](2)}, it contains no Al-Me functionality and has increased Lewis acidity at Al. Crystal structures and the NMR spectra of the aluminum complex (DIPH)AlMe and the bimetallic Al/Zr species reveal in both cases dimeric complexes. The crystal structure of [Cp*Zr-2(Me)OAl(DIPH)](2) shows a planar Al2O2 core and a terminal Cp*Zr-2(Me)O group. Ethylene polymerization in toluene was studied for the bimetallic complex with a variety of scavengers. Under comparable polymerization conditions, the methylalumoxane-activated species show high activities that are similar to those obtained with Cp*2ZrCl2 and Roesky's bimetallic complex Cp2Zr(Me)OAl(Me)(DIPP-nacnac), with a relatively narrow polydispersity index (2.47).

Original language	English
Pages (from-to)	2132-2138
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	12
DOIs	https://doi.org/10.1002/ejic.201500123
Publication status	Published - Apr-2015

Keywords

Sandwich complexes
Heterometallic complexes
Zirconium
Polymerization
Polyethylene
ZIEGLER-NATTA CATALYSTS
METHYL ALUMINOXANE CATALYST
OLEFIN POLYMERIZATION
PROPENE POLYMERIZATION
CHAIN TRANSFER
HOMOGENEOUS CATALYSTS
METALLOCENE CATALYSTS
TERT-BUTYLALUMINUM
DOUBLE ACTIVATION
ALUMINUM

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10.1002/ejic.201500123

Oxide-Bridged Heterobimetallic Aluminum-Zirconium Catalysts for EthyleneFinal publisher's version, 4.35 MBLicence: Taverne

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CCDC 1042668: Experimental Crystal Structure Determination
Boulho, C. (Contributor), Zijlstra, H. (Contributor) & Harder, S. (Contributor), University of Groningen, 8-Jan-2015
DOI: 10.5517/cc13zzgj
Dataset
CCDC 1042669: Experimental Crystal Structure Determination
Boulho, C. (Contributor), Zijlstra, H. (Contributor) & Harder, S. (Contributor), University of Groningen, 8-Jan-2015
DOI: 10.5517/cc13zzhk
Dataset

Cite this

@article{1364bb59adf84d6facd7b45e7e3ff4ab,

title = "Oxide-Bridged Heterobimetallic Aluminum/Zirconium Catalysts for Ethylene Polymerization",

abstract = "A bimetallic aluminum/zirconium complex Cp*Zr-2(Me)OAl(DIPH) [DIPH-H-2 = 3,3-bis(2-methylallyl)-(1,1-biphenyl)-2,2-diol; Cp* = C5Me5] was prepared in good yield by the reaction of (DIPH)AlMe with Cp*Zr-2(Me)OH. In contrast to Roesky's catalyst, Cp2Zr(Me)O(Me)Al(DIPP-nacnac) {DIPP-nacnac = CH[(CMe)(2,6-iPr(2)C(6)H(3)N)](2)}, it contains no Al-Me functionality and has increased Lewis acidity at Al. Crystal structures and the NMR spectra of the aluminum complex (DIPH)AlMe and the bimetallic Al/Zr species reveal in both cases dimeric complexes. The crystal structure of [Cp*Zr-2(Me)OAl(DIPH)](2) shows a planar Al2O2 core and a terminal Cp*Zr-2(Me)O group. Ethylene polymerization in toluene was studied for the bimetallic complex with a variety of scavengers. Under comparable polymerization conditions, the methylalumoxane-activated species show high activities that are similar to those obtained with Cp*2ZrCl2 and Roesky's bimetallic complex Cp2Zr(Me)OAl(Me)(DIPP-nacnac), with a relatively narrow polydispersity index (2.47).",

keywords = "Sandwich complexes, Heterometallic complexes, Zirconium, Polymerization, Polyethylene, ZIEGLER-NATTA CATALYSTS, METHYL ALUMINOXANE CATALYST, OLEFIN POLYMERIZATION, PROPENE POLYMERIZATION, CHAIN TRANSFER, HOMOGENEOUS CATALYSTS, METALLOCENE CATALYSTS, TERT-BUTYLALUMINUM, DOUBLE ACTIVATION, ALUMINUM",

author = "Cedric Boulho and Zijlstra, {Harmen S.} and Sjoerd Harder",

year = "2015",

month = apr,

doi = "10.1002/ejic.201500123",

language = "English",

pages = "2132--2138",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "WILEY-V C H VERLAG GMBH",

number = "12",

}

TY - JOUR

T1 - Oxide-Bridged Heterobimetallic Aluminum/Zirconium Catalysts for Ethylene Polymerization

AU - Boulho, Cedric

AU - Zijlstra, Harmen S.

AU - Harder, Sjoerd

PY - 2015/4

Y1 - 2015/4

N2 - A bimetallic aluminum/zirconium complex Cp*Zr-2(Me)OAl(DIPH) [DIPH-H-2 = 3,3-bis(2-methylallyl)-(1,1-biphenyl)-2,2-diol; Cp* = C5Me5] was prepared in good yield by the reaction of (DIPH)AlMe with Cp*Zr-2(Me)OH. In contrast to Roesky's catalyst, Cp2Zr(Me)O(Me)Al(DIPP-nacnac) {DIPP-nacnac = CH[(CMe)(2,6-iPr(2)C(6)H(3)N)](2)}, it contains no Al-Me functionality and has increased Lewis acidity at Al. Crystal structures and the NMR spectra of the aluminum complex (DIPH)AlMe and the bimetallic Al/Zr species reveal in both cases dimeric complexes. The crystal structure of [Cp*Zr-2(Me)OAl(DIPH)](2) shows a planar Al2O2 core and a terminal Cp*Zr-2(Me)O group. Ethylene polymerization in toluene was studied for the bimetallic complex with a variety of scavengers. Under comparable polymerization conditions, the methylalumoxane-activated species show high activities that are similar to those obtained with Cp*2ZrCl2 and Roesky's bimetallic complex Cp2Zr(Me)OAl(Me)(DIPP-nacnac), with a relatively narrow polydispersity index (2.47).

AB - A bimetallic aluminum/zirconium complex Cp*Zr-2(Me)OAl(DIPH) [DIPH-H-2 = 3,3-bis(2-methylallyl)-(1,1-biphenyl)-2,2-diol; Cp* = C5Me5] was prepared in good yield by the reaction of (DIPH)AlMe with Cp*Zr-2(Me)OH. In contrast to Roesky's catalyst, Cp2Zr(Me)O(Me)Al(DIPP-nacnac) {DIPP-nacnac = CH[(CMe)(2,6-iPr(2)C(6)H(3)N)](2)}, it contains no Al-Me functionality and has increased Lewis acidity at Al. Crystal structures and the NMR spectra of the aluminum complex (DIPH)AlMe and the bimetallic Al/Zr species reveal in both cases dimeric complexes. The crystal structure of [Cp*Zr-2(Me)OAl(DIPH)](2) shows a planar Al2O2 core and a terminal Cp*Zr-2(Me)O group. Ethylene polymerization in toluene was studied for the bimetallic complex with a variety of scavengers. Under comparable polymerization conditions, the methylalumoxane-activated species show high activities that are similar to those obtained with Cp*2ZrCl2 and Roesky's bimetallic complex Cp2Zr(Me)OAl(Me)(DIPP-nacnac), with a relatively narrow polydispersity index (2.47).

KW - Sandwich complexes

KW - Heterometallic complexes

KW - Zirconium

KW - Polymerization

KW - Polyethylene

KW - ZIEGLER-NATTA CATALYSTS

KW - METHYL ALUMINOXANE CATALYST

KW - OLEFIN POLYMERIZATION

KW - PROPENE POLYMERIZATION

KW - CHAIN TRANSFER

KW - HOMOGENEOUS CATALYSTS

KW - METALLOCENE CATALYSTS

KW - TERT-BUTYLALUMINUM

KW - DOUBLE ACTIVATION

KW - ALUMINUM

U2 - 10.1002/ejic.201500123

DO - 10.1002/ejic.201500123

M3 - Article

SN - 1434-1948

SP - 2132

EP - 2138

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 12

ER -

Oxide-Bridged Heterobimetallic Aluminum/Zirconium Catalysts for Ethylene Polymerization

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Keywords

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CCDC 1042668: Experimental Crystal Structure Determination

CCDC 1042669: Experimental Crystal Structure Determination

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