Asymmetric bis(formamidinate) group 4 complexes: Synthesis, structure and their reactivity in the polymerization of α-olefins.

Naveen V. Kulkarni; Tatyana Elkin; Boris Tumaniskii; Mark Botoshansky; Linda J.W. Shimon; Moris S. Eisen

doi:10.1021/om500345r

Asymmetric bis(formamidinate) group 4 complexes: Synthesis, structure and their reactivity in the polymerization of α-olefins.

Naveen V. Kulkarni, Tatyana Elkin, Boris Tumaniskii, Mark Botoshansky, Linda J.W. Shimon, Moris S. Eisen^*

^*Corresponding author for this work

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

26 Scopus citations

Abstract

A series of asymmetric formamidine ligands bearing different substituents with various steric and electronic properties on the nitrogen of the N-C-N motif were synthesized. Group 4 bis(formamidinate) dimethylamido, chloride, and benzyl complexes were studied using these asymmetric ligands and their solid-state structures and their behavior in solution were determined. These complexes were activated with MAO (methylalumoxane) or a combination of cocatalysts and tested in the polymerization of ethylene and propylene. A noticeable influence of the formamidine nitrogen substituents on the activity of the catalyst and properties of the obtained polymers was observed. Further, a plausible mechanism for the polymerization of propylene is presented derived from a combination of ESR-C₆₀ and MALDI-TOF trapping experiments which shed light on the nature of the active catalytic species.

Original language	English
Pages (from-to)	3119-3136
Number of pages	18
Journal	Organometallics
Volume	33
Issue number	12
DOIs	https://doi.org/10.1021/om500345r
State	Published - 23 Jun 2014
Externally published	Yes

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title = "Asymmetric bis(formamidinate) group 4 complexes: Synthesis, structure and their reactivity in the polymerization of α-olefins.",

abstract = "A series of asymmetric formamidine ligands bearing different substituents with various steric and electronic properties on the nitrogen of the N-C-N motif were synthesized. Group 4 bis(formamidinate) dimethylamido, chloride, and benzyl complexes were studied using these asymmetric ligands and their solid-state structures and their behavior in solution were determined. These complexes were activated with MAO (methylalumoxane) or a combination of cocatalysts and tested in the polymerization of ethylene and propylene. A noticeable influence of the formamidine nitrogen substituents on the activity of the catalyst and properties of the obtained polymers was observed. Further, a plausible mechanism for the polymerization of propylene is presented derived from a combination of ESR-C60 and MALDI-TOF trapping experiments which shed light on the nature of the active catalytic species.",

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doi = "10.1021/om500345r",

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T1 - Asymmetric bis(formamidinate) group 4 complexes

T2 - Synthesis, structure and their reactivity in the polymerization of α-olefins.

AU - Kulkarni, Naveen V.

AU - Elkin, Tatyana

AU - Tumaniskii, Boris

AU - Botoshansky, Mark

AU - Shimon, Linda J.W.

AU - Eisen, Moris S.

PY - 2014/6/23

Y1 - 2014/6/23

N2 - A series of asymmetric formamidine ligands bearing different substituents with various steric and electronic properties on the nitrogen of the N-C-N motif were synthesized. Group 4 bis(formamidinate) dimethylamido, chloride, and benzyl complexes were studied using these asymmetric ligands and their solid-state structures and their behavior in solution were determined. These complexes were activated with MAO (methylalumoxane) or a combination of cocatalysts and tested in the polymerization of ethylene and propylene. A noticeable influence of the formamidine nitrogen substituents on the activity of the catalyst and properties of the obtained polymers was observed. Further, a plausible mechanism for the polymerization of propylene is presented derived from a combination of ESR-C60 and MALDI-TOF trapping experiments which shed light on the nature of the active catalytic species.

AB - A series of asymmetric formamidine ligands bearing different substituents with various steric and electronic properties on the nitrogen of the N-C-N motif were synthesized. Group 4 bis(formamidinate) dimethylamido, chloride, and benzyl complexes were studied using these asymmetric ligands and their solid-state structures and their behavior in solution were determined. These complexes were activated with MAO (methylalumoxane) or a combination of cocatalysts and tested in the polymerization of ethylene and propylene. A noticeable influence of the formamidine nitrogen substituents on the activity of the catalyst and properties of the obtained polymers was observed. Further, a plausible mechanism for the polymerization of propylene is presented derived from a combination of ESR-C60 and MALDI-TOF trapping experiments which shed light on the nature of the active catalytic species.

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U2 - 10.1021/om500345r

DO - 10.1021/om500345r

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JO - Organometallics

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ER -

Asymmetric bis(formamidinate) group 4 complexes: Synthesis, structure and their reactivity in the polymerization of α-olefins.

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