Collaboration between Trinuclear Aluminum Complexes Bearing Bipyrazoles in the Ring-Opening Polymerization of ϵ-Caprolactone

Someswara Rao Kosuru; Feng Jie Lai; Yu Lun Chang; Chen Yu Li; Yi Chun Lai; Shangwu Ding; Kuo Hui Wu; Hsuan Ying Chen; Yung Han Lo

doi:10.1021/acs.inorgchem.1c01192

Collaboration between Trinuclear Aluminum Complexes Bearing Bipyrazoles in the Ring-Opening Polymerization of ϵ-Caprolactone

Someswara Rao Kosuru, Feng Jie Lai, Yu Lun Chang, Chen Yu Li, Yi Chun Lai, Shangwu Ding, Kuo Hui Wu, Hsuan Ying Chen, Yung Han Lo

Department of Chemistry

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Abstract

Trinuclear aluminum complexes bearing bipyrazoles were synthesized, and their catalytic activity for ϵ-caprolactone (CL) polymerization was investigated. DBu2Al3Me5 exhibited higher catalytic activity than did the dinuclear aluminum complex LBu2Al2Me4 (16 times as high for CL polymerization; [CL]:[DBu2Al3Me5]:[BnOH] = 100:0.5:5, [DBu2Al3Me5] = 10 mM, conversion 93% after 18 min at room temperature). Density functional theory calculations revealed a polymerization mechanism in which CL first approached the central Al atom and then moved to an external Al. The coordinated CL ring was opened because the repulsion of two tert-butyl groups on the ligands pushed an alkoxide initiator on an external Al to initiate CL. In these trinuclear Al catalysts, the central Al plays a role in monomer capture and then collaborates with the external Al to activate CL, accelerating polymerization.

Original language	English
Pages (from-to)	10535-10549
Number of pages	15
Journal	Inorganic Chemistry
Volume	60
Issue number	14
DOIs	https://doi.org/10.1021/acs.inorgchem.1c01192
State	Published - 19 Jul 2021

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10.1021/acs.inorgchem.1c01192

CCDC 1955471: Experimental Crystal Structure Determination
Kosuru, S. R. (Contributor), Lai, F. (Contributor), Chang, Y. (Contributor), Li, C. (Contributor), Lai, Y. (Contributor), Ding, S. (Contributor), Wu, K. (Contributor), Chen, H. (Contributor) & Lo, Y. (Contributor), Cambridge Crystallographic Data Centre, 2021
DOI: 10.5517/ccdc.csd.cc23mtq9, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc23mtq9&sid=DataCite
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title = "Collaboration between Trinuclear Aluminum Complexes Bearing Bipyrazoles in the Ring-Opening Polymerization of ϵ-Caprolactone",

abstract = "Trinuclear aluminum complexes bearing bipyrazoles were synthesized, and their catalytic activity for ϵ-caprolactone (CL) polymerization was investigated. DBu2Al3Me5 exhibited higher catalytic activity than did the dinuclear aluminum complex LBu2Al2Me4 (16 times as high for CL polymerization; [CL]:[DBu2Al3Me5]:[BnOH] = 100:0.5:5, [DBu2Al3Me5] = 10 mM, conversion 93% after 18 min at room temperature). Density functional theory calculations revealed a polymerization mechanism in which CL first approached the central Al atom and then moved to an external Al. The coordinated CL ring was opened because the repulsion of two tert-butyl groups on the ligands pushed an alkoxide initiator on an external Al to initiate CL. In these trinuclear Al catalysts, the central Al plays a role in monomer capture and then collaborates with the external Al to activate CL, accelerating polymerization.",

author = "Kosuru, {Someswara Rao} and Lai, {Feng Jie} and Chang, {Yu Lun} and Li, {Chen Yu} and Lai, {Yi Chun} and Shangwu Ding and Wu, {Kuo Hui} and Chen, {Hsuan Ying} and Lo, {Yung Han}",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = jul,

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doi = "10.1021/acs.inorgchem.1c01192",

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volume = "60",

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TY - JOUR

T1 - Collaboration between Trinuclear Aluminum Complexes Bearing Bipyrazoles in the Ring-Opening Polymerization of ϵ-Caprolactone

AU - Kosuru, Someswara Rao

AU - Lai, Feng Jie

AU - Chang, Yu Lun

AU - Li, Chen Yu

AU - Lai, Yi Chun

AU - Ding, Shangwu

AU - Wu, Kuo Hui

AU - Chen, Hsuan Ying

AU - Lo, Yung Han

PY - 2021/7/19

Y1 - 2021/7/19

N2 - Trinuclear aluminum complexes bearing bipyrazoles were synthesized, and their catalytic activity for ϵ-caprolactone (CL) polymerization was investigated. DBu2Al3Me5 exhibited higher catalytic activity than did the dinuclear aluminum complex LBu2Al2Me4 (16 times as high for CL polymerization; [CL]:[DBu2Al3Me5]:[BnOH] = 100:0.5:5, [DBu2Al3Me5] = 10 mM, conversion 93% after 18 min at room temperature). Density functional theory calculations revealed a polymerization mechanism in which CL first approached the central Al atom and then moved to an external Al. The coordinated CL ring was opened because the repulsion of two tert-butyl groups on the ligands pushed an alkoxide initiator on an external Al to initiate CL. In these trinuclear Al catalysts, the central Al plays a role in monomer capture and then collaborates with the external Al to activate CL, accelerating polymerization.

AB - Trinuclear aluminum complexes bearing bipyrazoles were synthesized, and their catalytic activity for ϵ-caprolactone (CL) polymerization was investigated. DBu2Al3Me5 exhibited higher catalytic activity than did the dinuclear aluminum complex LBu2Al2Me4 (16 times as high for CL polymerization; [CL]:[DBu2Al3Me5]:[BnOH] = 100:0.5:5, [DBu2Al3Me5] = 10 mM, conversion 93% after 18 min at room temperature). Density functional theory calculations revealed a polymerization mechanism in which CL first approached the central Al atom and then moved to an external Al. The coordinated CL ring was opened because the repulsion of two tert-butyl groups on the ligands pushed an alkoxide initiator on an external Al to initiate CL. In these trinuclear Al catalysts, the central Al plays a role in monomer capture and then collaborates with the external Al to activate CL, accelerating polymerization.

UR - http://www.scopus.com/inward/record.url?scp=85111096973&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.1c01192

DO - 10.1021/acs.inorgchem.1c01192

M3 - 期刊論文

C2 - 34232620

AN - SCOPUS:85111096973

SN - 0020-1669

VL - 60

SP - 10535

EP - 10549

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 14

ER -

Collaboration between Trinuclear Aluminum Complexes Bearing Bipyrazoles in the Ring-Opening Polymerization of ϵ-Caprolactone

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CCDC 1955471: Experimental Crystal Structure Determination

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