Supporting Data for “Why So Slow? Mechanistic Insights from Studies of a Poor Catalyst for Polymerization of ε-Caprolactone”

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2016
2016

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2016-11-27

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University of Minnesota

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Supporting Data for “Why So Slow? Mechanistic Insights from Studies of a Poor Catalyst for Polymerization of ε-Caprolactone”

Published Date

2017-05-18

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Tolman, William, B.
wtolman@umn.edu

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Experimental Data
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Abstract

These files contain data along with associated output from instrumentation supporting all results reported in Stasiw, D. E.; Mandal, M.; Neisen, B. D.; Mitchell, L. A.; Cramer, C. J.; Tolman, W. B. Why so slow? Mechanistic insights from studies of a poor catalyst for polymerization of ε-caprolactone. Inorg. Chem., 2016, 56, 725–728. Polymerization of ε-caprolactone (CL) using an aluminum alkoxide catalyst (1) designed to prevent unproductive trans binding was monitored at 110 °C in toluene-d8 by 1H NMR and the concentration versus time data fit to a first-order rate expression. A comparison of t1/2 for 1 to values for many other aluminum alkyl and alkoxide complexes shows much lower activity of 1 toward polymerization of CL. Density functional theory calculations were used to understand the basis for the slow kinetics. The optimized geometry of the ligand framework of 1 was found indeed to make CL trans binding difficult: no trans-bound intermediate could be identified as a local minimum. Nor were local minima for cis-bound precomplexes found, suggesting a concerted coordination–insertion for polymer initiation and propagation. The sluggish performance of 1 is attributed to a high-framework distortion energy required to deform the “resting” ligand geometry to that providing optimal catalysis in the corresponding transition-state structure geometry, thus suggesting a need to incorporate ligand flexibility in the design of efficient polymerization catalysts.. Corresponding author for experimental data is William B. Tolman (wtolman@umn.edu). Corresponding author for computational data is Christopher J. Cramer (cramer@umn.edu).

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Why So Slow? Mechanistic Insights from Studies of a Poor Catalyst for Polymerization of ε-Caprolactone Daniel E. Stasiw, Mukunda Mandal, Benjamin D. Neisen, Lauren A. Mitchell, Christopher J. Cramer, and William B. Tolman Inorganic Chemistry 2017 56 (2), 725-728. DOI: 10.1021/acs.inorgchem.6b02849
http://doi.org/10.1021/acs.inorgchem.6b02849

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Funding for this project was provided by the Center for Sustainable Polymers at the University of Minnesota, a National Science Foundation (NSF)-supported Center for Chemical Innovation (Grant CHE-1413862). The X-ray diffraction experiments were performed using a crystal diffractometer acquired through NSF-MRI Award CHE-1229400. The authors acknowledge the MSI at the University of Minnesota for providing resources that contributed to the research results.

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Suggested citation

Tolman, William, B; Cramer, Christopher, J; Stasiw, Daniel E; Mandal, Mukunda; Neisen, Benjamin D; Mitchell, Lauren A. (2017). Supporting Data for “Why So Slow? Mechanistic Insights from Studies of a Poor Catalyst for Polymerization of ε-Caprolactone”. Retrieved from the Data Repository for the University of Minnesota (DRUM), https://doi.org/10.13020/D6F60H.
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CSPStasiwMandalFiguresandTablesReadMe.txtDescription of Dataset12 KB
Figure 1 - Proposed mechanisms.cdxCDX File of Coordination-insertion ring opening transesterification polymerization mechanism8.25 KB
Figure 1 - Proposed mechanisms.jpegJPEG File of Coordination-insertion ring opening transesterification polymerization mechanism74.15 KB
Figure 2 Crystal Structure.zipCrystal structure files in CIF format596.74 KB
Figure 3 1H NMR Kinetics.zip1H NMR Kinetics data of CL to PCL polymerization for [CL]0 = 1 M4.88 MB
Figure 4 - Al Ligand Survey.cdxCDX File Comparison of literature polymerization rates for CL using Al-OR27.33 KB
Figure 4 - Al Ligand Survey.jpegJPEG File Comparison of literature polymerization rates for CL using Al-OR116.67 KB
Figure 5 Transition State Modeling.zipRaw Output Files for Density functional modeling of the key steps involved in the reaction pathway6.44 MB
Figure S1 1H 13C NMR of 1-OEt Catalyst.zipNMR data for 1H and 13C NMR of 1-OEt catalyst1.82 MB
Figure S2 1H NMR of Polymerization over Time.zip1H NMR stack plot of kinetic experiments5.69 MB
Figure S3 Summarized 1M _ 2M Kinetic Data.zipSummarized 1M and 2M NMR kinetics data12.63 MB
Figure S4 Linearized 1st Order 1M _ 2M Kinetic Data.zipLinearized 1st order kinetic rate for 1M and 2M data77.67 KB
ic6b02849_si_002.cifCIF X-ray crystallographic data1.71 MB
Structures for Table S2.cdxCDX File of Literature review of aluminum-alkoxide catalysts for ROP of CL509.57 KB
SEC Analysis.xlsxSize exclusion chromatography data.444.65 KB
CPS2_ArchivalVersion.zipArchive Version of the Excel Files (.csv format)1 MB

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