(E)-(Z) selectivity in the polymerization of 2-butene promoted by Ni(II) Brookhart-type catalysts

Giuseppe Milano; Gaetano Guerra; Mina Mazzeo; Claudio Pellecchia; Luigi Cavallo

doi:10.1021/ma048373y

(E)-(Z) selectivity in the polymerization of 2-butene promoted by Ni(II) Brookhart-type catalysts

Giuseppe Milano, Gaetano Guerra, Mina Mazzeo, Claudio Pellecchia, Luigi Cavallo^*

^*Corresponding author for this work

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

14 Scopus citations

Abstract

We offer a rationalization of the different reactivity observed in the polymerization of (E)-and (Z)-2-butene isomers with (α-diimine)Ni(II) complexes, known as "Brookhart catalysts". Quantum mechanics calculations suggest that the two isomers of 2-butene coordinate similarly to the metal and that the slower reactivity of the (Z) isomer is related to stronger steric interactions at the transition state for insertion into the Ni-chain bond. The similar coordination energies suggested that the presence of the (Z) isomer should not inhibit reactivity of the (E) isomer. This point was confirmed with polymerization experiments performed with a 40% (Z)-2-butene:60% (E)-2-butene mixture.

Original language	English (US)
Pages (from-to)	2072-2075
Number of pages	4
Journal	Macromolecules
Volume	38
Issue number	6
DOIs	https://doi.org/10.1021/ma048373y
State	Published - Mar 22 2005
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "(E)-(Z) selectivity in the polymerization of 2-butene promoted by Ni(II) Brookhart-type catalysts",

abstract = "We offer a rationalization of the different reactivity observed in the polymerization of (E)-and (Z)-2-butene isomers with (α-diimine)Ni(II) complexes, known as {"}Brookhart catalysts{"}. Quantum mechanics calculations suggest that the two isomers of 2-butene coordinate similarly to the metal and that the slower reactivity of the (Z) isomer is related to stronger steric interactions at the transition state for insertion into the Ni-chain bond. The similar coordination energies suggested that the presence of the (Z) isomer should not inhibit reactivity of the (E) isomer. This point was confirmed with polymerization experiments performed with a 40% (Z)-2-butene:60% (E)-2-butene mixture.",

author = "Giuseppe Milano and Gaetano Guerra and Mina Mazzeo and Claudio Pellecchia and Luigi Cavallo",

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T1 - (E)-(Z) selectivity in the polymerization of 2-butene promoted by Ni(II) Brookhart-type catalysts

AU - Milano, Giuseppe

AU - Guerra, Gaetano

AU - Mazzeo, Mina

AU - Pellecchia, Claudio

AU - Cavallo, Luigi

PY - 2005/3/22

Y1 - 2005/3/22

N2 - We offer a rationalization of the different reactivity observed in the polymerization of (E)-and (Z)-2-butene isomers with (α-diimine)Ni(II) complexes, known as "Brookhart catalysts". Quantum mechanics calculations suggest that the two isomers of 2-butene coordinate similarly to the metal and that the slower reactivity of the (Z) isomer is related to stronger steric interactions at the transition state for insertion into the Ni-chain bond. The similar coordination energies suggested that the presence of the (Z) isomer should not inhibit reactivity of the (E) isomer. This point was confirmed with polymerization experiments performed with a 40% (Z)-2-butene:60% (E)-2-butene mixture.

AB - We offer a rationalization of the different reactivity observed in the polymerization of (E)-and (Z)-2-butene isomers with (α-diimine)Ni(II) complexes, known as "Brookhart catalysts". Quantum mechanics calculations suggest that the two isomers of 2-butene coordinate similarly to the metal and that the slower reactivity of the (Z) isomer is related to stronger steric interactions at the transition state for insertion into the Ni-chain bond. The similar coordination energies suggested that the presence of the (Z) isomer should not inhibit reactivity of the (E) isomer. This point was confirmed with polymerization experiments performed with a 40% (Z)-2-butene:60% (E)-2-butene mixture.

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U2 - 10.1021/ma048373y

DO - 10.1021/ma048373y

M3 - Article

AN - SCOPUS:15944406832

SN - 0024-9297

VL - 38

SP - 2072

EP - 2075

JO - Macromolecules

JF - Macromolecules

IS - 6

ER -

(E)-(Z) selectivity in the polymerization of 2-butene promoted by Ni(II) Brookhart-type catalysts

Abstract

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