1. Title of Dataset Supporting Data for “Why So Slow? Mechanistic Insights from Studies of a Poor Catalyst for Polymerization of ε-Caprolactone” 2. Author Information Principal Investigator Contact Information Name: William B. Tolman Institution:University of Minnesota Address: 207 Pleasant Street SE, Minneapolis, Minnesota 55455 Email: wtolman@umn.edu Principal Investigator Contact Information Name: Christopher J. Cramer Institution: University of Minnesota Address: 207 Pleasant Street SE, Minneapolis, Minnesota 55455 Email: cramer@umn.edu Associate or Co-investigator Contact Information Name: Daniel E. Stasiw Institution: University of Minnesota Address: 207 Pleasant Street SE, Minneapolis, Minnesota 55455 Email: dstasiw@umn.edu Associate or Co-investigator Contact Information Name: Mukunda Mandal Institution: University of Minnesota Address: 207 Pleasant Street SE, Minneapolis, Minnesota 55455 Email: manda071@umn.edu Associate or Co-investigator Contact Information Name: Benjamin D. Neisen Institution: University of Minnesota Address: 207 Pleasant Street SE, Minneapolis, Minnesota 55455 Email:neise010@umn.edu Associate or Co-investigator Contact Information Name: Lauren A. Mitchell Institution: University of Minnesota Address: 207 Pleasant Street SE, Minneapolis, Minnesota 55455 Email: lmitchel@umn.edu 3. Date of data collection (single date, range, approximate date): 2016 4. Geographic location of data collection (where was data collected?): University of Minnesota 5. Information about funding sources that supported the collection of the data: 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. -------------------------- SHARING/ACCESS INFORMATION -------------------------- 1. Licenses/restrictions placed on the data: None 2. Links to publications that cite or use the data: Stasiw, D. E., Mandal, M., Neisen, B. D., Mitchell, L. A., Cramer, C. J., Tolman, W. B. Inorg. Chem., 2017, 56 (2), pp 725–728. DOI: 10.1021/acs.inorgchem.6b02849 3. Links to other publicly accessible locations of the data: http://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.6b02849 CIF file available 4. Links/relationships to ancillary data sets: None 5. Was data derived from another source? No 6. Recommended citation for the data: 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, https://doi.org/10.13020/D6F60H. Purpose Statement: This text document describes the files and their relationship to each other within the Figures and Tables folder. The document is organized like the folder in terms of Figure number or Table number. General Notes: Files starting with “DES” indicate lab book number by roman numerals (I or II) followed by page number and (occasionally) followed by experiment number on that page (i.e. “DESII-38-1” is DES book 2, page 38, experiment 1). Files contained within folders are indicated below the folder name with a preceding tab before the file name. File: Figure 1 - Proposed mechanisms.cdx Figure 1 - Proposed mechanisms.pdf Short Description: Coordination-insertion ring opening transesterification polymerization mechanism File Relationships / Notes: Chemdraw file used to make line bond drawings for Figure 1 Folder: Figure 2 Crystal Structure Short Description: Crystal structure files Files Contained: 1. 16003_final_cifreport.html 2. 16003_final_cifreport.pdf 3. 16003_final.cif File Relationships / Notes: The Crystallographic Information File (.cif) file contains the crystallographic information used to create images for Figure 2. The cif report generated as a service of the International Union of Crystallography describes the quality of the .cif file at the time of publication. Folder: Figure 3 1H NMR Kinetics Short Description: 1H NMR Kinetics of CL to PCL polymerization for [CL]0 = 1 M Files Contained: 1. DESII-38-1 AlOEtTMTAA CL - 1 (folder) a. Folders numbered 1-8 (NMR data) 2. DESII-38-1 AlOEtTMTAA + CL.xlsx 3. DESII-38-1 AlOEtTMTAA + CL 1st Order Kinetics.cps 4. DESII-38-1 AlOEtTMTAA + CL.txt 5. Figure 3 - DESII-38 COPASI in minutes.jpg 6. Figure 3 - DESII-38 COPASI in seconds.jpg File Relationships / Notes: The folder “DESII-38-1 AlOEtTMTAA CL - 1” contains the 8 raw NMR (nuclear magnetic resonance spectroscopy) experiments used for creation of this figure. The excel file converts 1H NMR integration data to concentration. The .txt file is the time and concentration data taken from the excel file. Using the text file as input, the .cps file is a COPASI file for the concentration versus time data fit to a rate equation. COPASI is a free software available from http://copasi.org/. Note: The fit data can be found in the kinetics summary file “Figure S3 - All Kinetic Data (1M and 2M).xlsx” found in the folder “Figure S3 Summarized 1M _ 2M Kinetic Data”. Files: Figure 4 - Al Ligand Survey.cdx Figure 4 - Al Ligand Survey.jpeg Short Description: Comparison of literature polymerization rates for CL using Al-OR File Relationships / Notes: Line bond drawing chemdraw file used to create figure 4. t1/2 data collected or calculated [(t1/2) = ln(2) / k] from Table S1. Folder: Figure 5 Transition State Modeling Short Description: Density functional modeling of the key steps involved in the reaction pathway. Files Contained: 1. 5coord_intd_OptFrq.out 2. al_tmtaa_catalyst.Frq.out 3. al_tmtaa_catalyst_optimization.out 4. cl_ring_open_pdt_OptFrq.out 5. cl_toluene_freq.out 6. cl_toluene_opt.out 7. computational Part of SI.pdf 8. Data For Inorg. Chem. 2017, 56, 725.xlsx 9. Figure 5 - [TS DFT] CL project progress_April_2016.pdf 10. reactant_frame_spe.out 11. tmtaa_CL_precomplex_optfreq.out 12. ts1_frame_spe.out 13. ts1_frequency.out 14. ts1_geom_optimization.out 15. ts2_OptFrq.out File Relationships / Notes: The files are raw data output files (for three key steps, geometry optimization of a given species, followed by its frequency analysis, and finally its refined electronic energy calculation), obtained using Gaussian 09 Program package. Figure 5 can be thought of as an excerpt of all these raw data files. Computational details are discussed in the supplemental file named “Computational Part Of SI.pdf”. Folder: Figure S1 1H 13C NMR of 1-OEt Catalyst Short Description: 1H and 13C NMR of 1-OEt catalyst. Files Contained: 1. DESI-71 AlOEtTMTAA HD-500 1H-NMR wtodes-160505-14 [folder] 2. DESI-71 AlOEtTMTAA HD-500 13C-NMR wtodes-160505-14 [folder] 3. DESI-71 AlOEtTMTAA HD-500 1H-NMR wtodes-160505-14.011.esp 4. DESI-71 AlOEtTMTAA HD-500 13C-NMR wtodes-160505-14.011.esp 5. Figure S1 - NMR of 1-OEt.pptx 6. Figure S1 - NMR of 1-OEt.pdf File Relationships / Notes: The folders contain the NMR data for the 1H and 13C characterization. The .fid file can be opened in any NMR analysis software. The .acqus file contains information about the parameters. The .esp files are ACDLabs NMR Processor worked up raw data. Folder: Figure S2 1H NMR of Polymerization over Time Short Description: 1H NMR stack plot of kinetic experiments Files Contained: 1. Figure S2 - NMR time lapse stack plot.pptx 2. DESII-62 AlOEtTMTAA 2M CL 1.001.001.1r.esp 3. Figure S2 - NMR time lapse stack plot.png File Relationships / Notes: Raw data used to create Figure S2 is contained in folder “Figure S3 / DESII-62-1 AlOEtTMTAA 2M CL 1H NMR Kinetics Data”. The esp file is the NMR data worked up and overlaid in ACDLabs NMR Processor overlaid to make the picture in the pptx file. Folder: Figure S3 Summarized 1M & 2M Kinetic Data Short Description: Summarized 1M and 2M kinetics data. Files Contained: 1. DESII-37-1 AlOEtTMTAA 1M CL 1H NMR Kinetics Data [folder] a. DESII-37-1 AlOEtTMTAA CL Raw NMR Data [folder] [folders numbered 1-6 (NMR data)] b. DESII-37 AlOEtTMTAA CL 1st Order.cps c. DESII-37 AlOEtTMTAA CL COPASI 1st order output.txt d. DESII-37 AlOEtTMTAA CL COPASI input.txt e. DESII-37 AlOEtTMTAA NMR Integration to Concentration.xlsx f. DESII-37-1 COPASI parameters output.txt 2. DESII-62-1 AlOEtTMTAA 2M CL 1H NMR Kinetics Data (Folder) a. DESII-62-1 AlOEtTMTAA 2M CL Raw NMR Data (Folder) [folders numbered 1-9 (NMR data)] b. ]DESII-62-1 1st Order Fitting.cps c. DESII-62-1 AlOEtTMTAA 2M CL NMR Integration to Concentration.xlsx d. DESII-62-1 CL vs PCL COPASI input.txt e. DESII-62-1 COPASI Fitting output.txt f. DESII-62-1 COPASI parameters output.txt 3. DESII-62-2 AlOEtTMTAA 2M CL 1H NMR Kinetics Data [folder] a. DESII-62-2 AlOEtTMTAA 2M CL Raw NMR Data” [folder] [folders numbered 1-9 (NMR data)] b. DESII-62-2 1st Order.cps c. DESII-62-2 AlOEtTMTAA 2M CL Integration to Concentration.xlsx d. DESII-62-2 CL vs PCL COPASI input.txt e. DESII-62-2 COPASI Fitting output.txt f. DESII-62-2 COPASI parameters output.txt 4. Figure S3 - All Kinetic Data (1M and 2M).xlsx 5. Figure S3 - DESII-62-1 2M COPASI Fit.jpg File Relationships / Notes: The excel file “Figure S3 - All Kinetic Data (1M and 2M).xlsx” simply collates the kinetic data from the 3 folders and the data for DESII-38-1 in folder “Figure 3 / DESII-38-1 AlOEtTMTAA CL - 1”. This file is split into two tabs: 1M data and 2M data. In both sets the shorter column is the experimental concentration data versus time. The longer columns are the COPASI best fit lines to the experimental data. In the three folders of raw data there are 5 files and a folder of raw NMR data. The xlsx file converts raw NMR data to concentration through comparison to the integration of an internal standard. The concentration versus time data is converted into a “[...] COPASI input.txt” file for use in the COPASI global fitting program. The COPASI fit itself is saved as a .cps file generated with COPASI 4.15 (Build 95) (http://www.copasi.org) at 2016-09-22 20:11:56. The .csp file can be opened as XML with a text editor. The best fit lines from the COPASI fit are saved as “[...] COPASI Fitting output.txt” files and the fit parameters for these fits are saved as “[...] COPASI parameters output.txt” files. Folder: Figure S4 Linearized 1st Order 1M & 2M Kinetic Data Short Description: Linearized 1st order kinetic rate for 1M and 2M data. Files Contained: 1. Linearized Kinetic Fits.xlsx 2. Fig S4 Linearized Kinetic Fits.png File Relationships / Notes: Concentration and time data for this xlsx file can be found in the “Figure S3 / Figure S3 - All Kinetic Data (1M and 2M).xlsx” file. Time in seconds was converted to minutes and concentration linearized by performing: LN( [CL]0 / [CL]t ) where [CL]0 = 1 for DESII-37 and DESII-38, [CL]0 = 2 for DESII-61-1 and DESII-61-2, and [CL]t is the respective experimentally determined concentration at each time point. File: ic6b02849_si_002.cif Short Description: X-ray crystallographic data in CIF format Files Contained: Table S1 contains crystallographic data that can be extracted from the .cif file. File: Structures for Table S2.cdx Short Description: Literature review of aluminum-alkoxide catalysts for ROP of CL. File Relationships / Notes: I had to redraw most of the catalysts for Table S2 in the supporting information for this paper. This chemdraw file contains those re-drawings. File: SEC Analysis.xlsx Short Description: Size exclusion chromatography data. File Relationships / Notes: This excel file contains the raw data and calibration for molecular weight and polydispersity data reported in the paper.