Heterolepic β ‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide

S. Ghosh; P.M. Schafer; D. Dittrich; C. Scheiper; P. Steiniger; G. Fink; A.N. Ksiazkiewicz; A. Tjaberings; C. Wolper; A.H. Groschel; A. Pich; S. Herres-Pawlis; S. Schulz

doi:10.1002/open.201900203

Heterolepic β ‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide

S. Ghosh
, P.M. Schafer
, D. Dittrich
, C. Scheiper
, P. Steiniger
, G. Fink
, A.N. Ksiazkiewicz
, A. Tjaberings
, C. Wolper
, A.H. Groschel
, A. Pich
, S. Herres-Pawlis^*
, S. Schulz^*

^*Corresponding author for this work

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

Abstract

Zinc phenoxide complexes (LZnOAr)-Zn-1 1-4 (L-1=Me2NC2H4NC(Me)CHC(Me)O) and (LZnOAr)-Zn-2 5-8 (L-2=Me2NC3H6NC(Me)CHC(Me)O) with donor-functionalized beta-ketoiminate ligands (L-1/2) and OAr substituents (Ar=Ph 1, 5; 2,6-Me-2-C6H3 2, 6; 3,5-Me-2-C6H3 3, 7; 4-Bu-C6H4 4, 8) with tuneable electronic and steric properties were synthesized and characterized. 1-8 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl3 solution. 1-8 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH2Cl2 at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (M-n) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L-LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled H-1-NMR analyses of polylactic acid (PLA) formed with rac-LA proved isotactic enrichment of the PLA microstructure.

Original language	English
Pages (from-to)	951-960
Number of pages	10
Journal	Chemistry Open
Volume	8
Issue number	7
DOIs	https://doi.org/10.1002/open.201900203
Publication status	Published - 1 Jul 2019

Keywords

aluminum complexes
coordination chemistry
diastereoselective synthesis
epsilon-caprolactone
ketoiminate
lactide
lewis pairs
magnesium
polymerization reactions
single-site catalysts
stereoselective polymerization
structural-characterization
substituent effects
tridentate ketiminate ligands
zinc
COORDINATION CHEMISTRY
STRUCTURAL-CHARACTERIZATION
ALUMINUM COMPLEXES
STEREOSELECTIVE POLYMERIZATION
TRIDENTATE KETIMINATE LIGANDS
LEWIS PAIRS
MAGNESIUM
EPSILON-CAPROLACTONE
DIASTEREOSELECTIVE SYNTHESIS
SINGLE-SITE CATALYSTS

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10.1002/open.201900203Licence: CC BY-NC-ND

CCDC 1900057 : Experimental Crystal Structure Determination
Ghosh, S. (Creator), Schäfer, P. M. (Contributor), Dittrich, D. (Contributor), Scheiper, C. (Contributor), Steiniger, P. (Contributor), Fink, G. (Contributor), Ksiazkiewicz, A. N. (Contributor), Tjaberings, A. (Contributor), Wölper, C. (Contributor), Gröschel, A. H. (Contributor), Pich, A. (Contributor), Herres-Pawlis, S. (Contributor) & Schulz, S. (Contributor), Cambridge Crystallographic Data Centre, 27 Feb 2019
DOI: 10.5517/ccdc.csd.cc21s556
Dataset/Software: Dataset
CCDC 1900055 : Experimental Crystal Structure Determination
Ghosh, S. (Creator), Schäfer, P. M. (Contributor), Dittrich, D. (Contributor), Scheiper, C. (Contributor), Steiniger, P. (Contributor), Fink, G. (Contributor), Ksiazkiewicz, A. N. (Contributor), Tjaberings, A. (Contributor), Wölper, C. (Contributor), Gröschel, A. H. (Contributor), Pich, A. (Contributor), Herres-Pawlis, S. (Contributor) & Schulz, S. (Contributor), Cambridge Crystallographic Data Centre, 27 Feb 2019
DOI: 10.5517/ccdc.csd.cc21s534
Dataset/Software: Dataset
CCDC 1900058 : Experimental Crystal Structure Determination
Ghosh, S. (Creator), Schäfer, P. M. (Contributor), Dittrich, D. (Contributor), Scheiper, C. (Contributor), Steiniger, P. (Contributor), Fink, G. (Contributor), Ksiazkiewicz, A. N. (Contributor), Tjaberings, A. (Contributor), Wölper, C. (Contributor), Gröschel, A. H. (Contributor), Pich, A. (Contributor), Herres-Pawlis, S. (Contributor) & Schulz, S. (Contributor), Cambridge Crystallographic Data Centre, 27 Feb 2019
DOI: 10.5517/ccdc.csd.cc21s567
Dataset/Software: Dataset

Cite this

Ghosh, S., Schafer, P. M., Dittrich, D., Scheiper, C., Steiniger, P., Fink, G., Ksiazkiewicz, A. N., Tjaberings, A., Wolper, C., Groschel, A. H., Pich, A., Herres-Pawlis, S., & Schulz, S. (2019). Heterolepic β ‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide. Chemistry Open, 8(7), 951-960. https://doi.org/10.1002/open.201900203

@article{a1ffb6fb87884f48b45154915446e9d1,

title = "Heterolepic β ‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide",

abstract = "Zinc phenoxide complexes (LZnOAr)-Zn-1 1-4 (L-1=Me2NC2H4NC(Me)CHC(Me)O) and (LZnOAr)-Zn-2 5-8 (L-2=Me2NC3H6NC(Me)CHC(Me)O) with donor-functionalized beta-ketoiminate ligands (L-1/2) and OAr substituents (Ar=Ph 1, 5; 2,6-Me-2-C6H3 2, 6; 3,5-Me-2-C6H3 3, 7; 4-Bu-C6H4 4, 8) with tuneable electronic and steric properties were synthesized and characterized. 1-8 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl3 solution. 1-8 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH2Cl2 at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (M-n) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L-LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled H-1-NMR analyses of polylactic acid (PLA) formed with rac-LA proved isotactic enrichment of the PLA microstructure.",

keywords = "aluminum complexes, coordination chemistry, diastereoselective synthesis, epsilon-caprolactone, ketoiminate, lactide, lewis pairs, magnesium, polymerization reactions, single-site catalysts, stereoselective polymerization, structural-characterization, substituent effects, tridentate ketiminate ligands, zinc, COORDINATION CHEMISTRY, STRUCTURAL-CHARACTERIZATION, ALUMINUM COMPLEXES, STEREOSELECTIVE POLYMERIZATION, TRIDENTATE KETIMINATE LIGANDS, LEWIS PAIRS, MAGNESIUM, EPSILON-CAPROLACTONE, DIASTEREOSELECTIVE SYNTHESIS, SINGLE-SITE CATALYSTS",

author = "S. Ghosh and P.M. Schafer and D. Dittrich and C. Scheiper and P. Steiniger and G. Fink and A.N. Ksiazkiewicz and A. Tjaberings and C. Wolper and A.H. Groschel and A. Pich and S. Herres-Pawlis and S. Schulz",

note = "Funding Information: Financial support by Evonik Industries (P.S., A.T., A.H.G.) and the University of Duisburg Essen (St.S.) is acknowledged. A.H.G. is grateful for financial support from the DFG through the Emmy-Noether Program (No. 376920678). P.M.S. thanks the Hanns-Seidel-Foundation (fellowship) for funding (Bundesministerium f?r Bildung und Forschung, BMBF). S.H.-P. thanks Total Corbion PLA for lactide donations. Publisher Copyright: {\textcopyright} 2019 The Authors. Published by Wiley-VCH Verlag GmbH \& Co. KGaA.",

year = "2019",

month = jul,

day = "1",

doi = "10.1002/open.201900203",

language = "English",

volume = "8",

pages = "951--960",

journal = "Chemistry Open",

issn = "2191-1363",

publisher = "Wiley-VCH Verlag",

number = "7",

}

Ghosh, S, Schafer, PM, Dittrich, D, Scheiper, C, Steiniger, P, Fink, G, Ksiazkiewicz, AN, Tjaberings, A, Wolper, C, Groschel, AH, Pich, A, Herres-Pawlis, S & Schulz, S 2019, 'Heterolepic β ‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide', Chemistry Open, vol. 8, no. 7, pp. 951-960. https://doi.org/10.1002/open.201900203

TY - JOUR

T1 - Heterolepic β ‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide

AU - Ghosh, S.

AU - Schafer, P.M.

AU - Dittrich, D.

AU - Scheiper, C.

AU - Steiniger, P.

AU - Fink, G.

AU - Ksiazkiewicz, A.N.

AU - Tjaberings, A.

AU - Wolper, C.

AU - Groschel, A.H.

AU - Pich, A.

AU - Herres-Pawlis, S.

AU - Schulz, S.

N1 - Funding Information: Financial support by Evonik Industries (P.S., A.T., A.H.G.) and the University of Duisburg Essen (St.S.) is acknowledged. A.H.G. is grateful for financial support from the DFG through the Emmy-Noether Program (No. 376920678). P.M.S. thanks the Hanns-Seidel-Foundation (fellowship) for funding (Bundesministerium f?r Bildung und Forschung, BMBF). S.H.-P. thanks Total Corbion PLA for lactide donations. Publisher Copyright: © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

PY - 2019/7/1

Y1 - 2019/7/1

N2 - Zinc phenoxide complexes (LZnOAr)-Zn-1 1-4 (L-1=Me2NC2H4NC(Me)CHC(Me)O) and (LZnOAr)-Zn-2 5-8 (L-2=Me2NC3H6NC(Me)CHC(Me)O) with donor-functionalized beta-ketoiminate ligands (L-1/2) and OAr substituents (Ar=Ph 1, 5; 2,6-Me-2-C6H3 2, 6; 3,5-Me-2-C6H3 3, 7; 4-Bu-C6H4 4, 8) with tuneable electronic and steric properties were synthesized and characterized. 1-8 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl3 solution. 1-8 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH2Cl2 at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (M-n) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L-LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled H-1-NMR analyses of polylactic acid (PLA) formed with rac-LA proved isotactic enrichment of the PLA microstructure.

AB - Zinc phenoxide complexes (LZnOAr)-Zn-1 1-4 (L-1=Me2NC2H4NC(Me)CHC(Me)O) and (LZnOAr)-Zn-2 5-8 (L-2=Me2NC3H6NC(Me)CHC(Me)O) with donor-functionalized beta-ketoiminate ligands (L-1/2) and OAr substituents (Ar=Ph 1, 5; 2,6-Me-2-C6H3 2, 6; 3,5-Me-2-C6H3 3, 7; 4-Bu-C6H4 4, 8) with tuneable electronic and steric properties were synthesized and characterized. 1-8 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl3 solution. 1-8 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH2Cl2 at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (M-n) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L-LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled H-1-NMR analyses of polylactic acid (PLA) formed with rac-LA proved isotactic enrichment of the PLA microstructure.

KW - aluminum complexes

KW - coordination chemistry

KW - diastereoselective synthesis

KW - epsilon-caprolactone

KW - ketoiminate

KW - lactide

KW - lewis pairs

KW - magnesium

KW - polymerization reactions

KW - single-site catalysts

KW - stereoselective polymerization

KW - structural-characterization

KW - substituent effects

KW - tridentate ketiminate ligands

KW - zinc

KW - COORDINATION CHEMISTRY

KW - STRUCTURAL-CHARACTERIZATION

KW - ALUMINUM COMPLEXES

KW - STEREOSELECTIVE POLYMERIZATION

KW - TRIDENTATE KETIMINATE LIGANDS

KW - LEWIS PAIRS

KW - MAGNESIUM

KW - EPSILON-CAPROLACTONE

KW - DIASTEREOSELECTIVE SYNTHESIS

KW - SINGLE-SITE CATALYSTS

U2 - 10.1002/open.201900203

DO - 10.1002/open.201900203

M3 - Article

SN - 2191-1363

VL - 8

SP - 951

EP - 960

JO - Chemistry Open

JF - Chemistry Open

IS - 7

ER -

Heterolepic β ‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide

Abstract

Keywords

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Datasets

CCDC 1900057 : Experimental Crystal Structure Determination

CCDC 1900055 : Experimental Crystal Structure Determination

CCDC 1900058 : Experimental Crystal Structure Determination

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