Readme created by Tedd C. Wiessner and Samuel Asiedu Fosu ------------------- GENERAL INFORMATION ------------------- Title of Dataset: Supporting Data for Ligand effects on Decarbonylation of Palladium-acyl Complexes Author Information: Principal Investigator Contact Information Name: William B. Tolman Institution: Washington University in Saint Louis Address: Department of Chemistry and Center for Sustainable Polymers, Washington University in St. Louis, One Brookings Hall, Campus Box 1134, St. Louis, MO 63130-4899 Email: wbtolman@wustl.edu Principal Investigator Contact Information Name: Bess Vlaisavljevich Institution: University of South Dakota Address: 414 E Clark St. Vermillion, SD 67069 Email: Bess.Vlaisavljevich@usd.edu Associate or Co-investigator Contact Information Name: Tedd C. Wiessner Institution: Washington University in St. Louis Address: One Brookings Hall, Campus Box 1134, St. Louis, MO 63130-4899 Email: tedd@wustl.edu Associate or Co-investigator Contact Information Name: Samuel Asiedu Fosu Institution: University of South Dakota Address: 414 E Clark St. Vermillion, SD 67069 Email: Samuel.Fosu@coyotes.usd.edu Associate or Co-investigator Contact Information Name: Riffat Parveen Institution: University of South Dakota Address: 414 E Clark St. Vermillion, SD 67069 Email: Riffat.Parveen@usd.edu Associate or Co-investigator Contact Information Name: Nigam P. Rath Institution: University of Missouri-St. Louis Address: One University Boulevard, St. Louis, MO 63121 Email: rathn@umsl.edu Date of data collection (single date, range, approximate date): 12/18/2020-08/24/2020 Geographic location of data collection (where was data collected?): Computations were carried out at the University of South Dakota; X-ray Crystallography data was obtained at the University of Missouri, Saint Louis; All other experimental data were collected at Washington University in Saint Louis. Information about funding sources that supported the collection of the data: This research was supported by a grant from the National Science Foundation through the Center for Sustainable Polymers (grant CHE-1413862). -------------------------- SHARING/ACCESS INFORMATION -------------------------- 1. Licenses/restrictions placed on the data: CC0 1.0 Universal 2. Links to publications that cite or use the data: Wiessner, T. C.; Fosu, S. A.; Parveen, R.; Rath, N. P.; Vlasavljevich, B.; Tlman, W. B. Ligand effects on decarbonylation of palladium-acyl complexes. Organometallics, 2020 Article ASAP. https://doi.org/10.1021/acs.organomet.0c00584 3. Links to other publicly accessible locations of the data: None 4. Links/relationships to ancillary data sets: None 5. Was data derived from another source? No 6. Recommended citation for the data: Wiessner, Tedd C; Fosu, Samuel A; Parveen, Riffat; Vlaisavljevich, Bess; Tolman, William B; Rath, Nigam. (2020). Supporting Information for Ligand effects on Decarbonylation of Palladium-acyl Complexes. Retrieved from the Data Repository for the University of Minnesota, https://doi.org/10.13020/xpa3-w249. --------------------- DATA & FILE OVERVIEW --------------------- Purpose Statement: General Notes: There are 4 folders that are labeled according to the type of data they hold. These folders include Spectral Data (fid), crystallography (cif), images (jpeg), ……. fab, fcf, hkl, pcf, res files are for verification and experimental format. For Spectral Data data the subfolders are organized into folders for relevant comparisons. That is the characterizations of each complex are within one folder, as are Spectral Data data relevant to thermolysis reactions, additive reactions, and kinetic studies. Within each of these folders the data for each complex has its own folder (Complex 1, 2, 3, or 2+). Labeling of data matches the reported labels used within the SI and the manuscript. Subfolders to the folder of Images/ChemDraws are separated into two subfolders: one for the Supplemental Information and one for the main body of the manuscript. Files Contained: There are four folders separated by the type of data they contain (listed below). Spectral Data is included as a single main folder within which it is separated for each reaction (thermolysis or additive reactions) reported, as well as, for characterizations (proton, carbon and phosphorous NMR) of all reported complexes. A subfolder for Spectral Data used to determine the kinetics of the reported halide abstraction are also included for each separate trial reported, matching the nomenclature reported within the SI. Within each folder is a second subfolder that separates out the data pertaining to each individual complex reported. The .fid file for each Spectral Data can be opened within any NMR analysis software (e.g. MNOVA, TopSpin, ACDlabs etc.). Folder listing (all folders contain fid, log, procpar and text files): * Spectral Data RMS-ESI of 2+ BF4 as dimer.png HRMS-ESI of 2+ BF4 as monomer.png HRMS-ESI of 2+ SbF6 as dimer.png HRMS-ESI of 2+ SbF6 as monomer.png o Additive Reactions * Complex 1 * Complex 1 AgBF4 * Complex 1 AgSbF6 * Complex 1 Al(OtBu)3 * Complex 1 Diisopropylthiourea * Complex 1 KBArf * Complex 1 LaCl3 * Complex 1 Mg(OAc)2 * Complex 1 NaBArf * Complex 1 NaBF4 * Complex 1 NaPF6 * Complex 1 no additive * Complex 1 Schreiner’s Thiourea * Complex 1 Thiourea * Complex 1 Triazobicyclohecene * Complex 1 Zn(OAc)2 * Complex 1 Zn(Cl)2 * Complex 1 ZnO * Complex 2 * Complex 2 AgBF4 * Complex 2 AgOTf * Complex 2 Diisopropylthiourea * Complex 2 NaBArf * Complex 2 NaSbF6 * Complex 2 Zn(OAc)2 * Complex 2 Zn(Cl)2 * Complex 2 ZnO * Complex 2+ * Complex 2+ Diisopropylthiourea * Complex 2+ Zn(OAc)2 * Complex 2+ Zn(Cl)2 * Complex 2+ ZnO * Complex 3 * Complex 3 AgBF4 * Complex 3 Diisopropylthiourea * Complex 3 NaBArf * Complex 3 NaSbF6 * Complex 3 Zn(OAc)2 * Complex 3 Zn(Cl)2 * Complex 3 ZnO * Formation and decay of 4+ over time o Complexes Characterization * Pd dppe (complex 3) * Pd-acyl-dppe-DCM-1H * Pd-acyl-dppe-DCM-13C * Pd-acyl-dppe-DCM-31P * Pd dppe BF4 (complex 3+) * Pd-acyl-dppe-BF4-CD3CN-1H * Pd dppe BF4 (complex 4+) * Pd alkyl dppe Carbon * Pd alkyl dppe COSY * Pd alkyl dppe Proton * Pd PPh3 (complex 2) * Pd-acyl-PPh3-1H * Pd-acyl-PPh3-13C * Pd-acyl-PPh3-31P * Pd PPh3 SbF6 cation (Complex 2+ SbF6) * Pd-acyl-PPh3-SbF6-DCM-1H * Pd-acyl-PPh3-SbF6-DCM-13C * Pd-acyl-PPh3-SbF6-DCM-31P * Pd PtBu3 (complex 1) * Pd-acyl-PtBu3-1H * Pd-acyl-PtBu3-13C * Pd-acyl-PtBu3-31P o Kinetic Data * NaBArf = 0.012 * I(I) * I(II) * I(III) * NaBArf = 0.014 * H(I) * H(II) * H(III) * NaBArf = 0.019 * G(I) * G(II) * G(III) * NaBArf = 0.023 * F(I) * F(II) * F(III) * NaBArf = 0.028 * E(I) * E(II) * E(III) * NaBArf = 0.037 * D(I) * D(II) * D(III) * NaBArf = 0.042 * C(I) * C(II) * C(III) * NaBArf = 0.047 * B(I) * B(II) * B(III) * NaBArf = 0.056 * A(I) * A(II) * A(III) * CSV file: Plot data for kinetics (time points, Ln[1] * Excel file: Plot data for kinetics (time points, Ln[1] o Protonated phosphine * Deuterated PtBu3-D-1H * Deuterated PtBu3-D-31P * Protonated PtBu3-H-1H * Protonated PtBu3-H-31P o Thermolysis Reactions * Complex 1 * Complex 1 40C MeCN * Complex 146C Bn * Complex 1 46C CDCl3 * Complex 1 46C MeCN * Complex 1 46C THF * Complex 1 54C DMSO * Complex 1 54C THF * Complex 2 * Complex 2, 54C DMSO * Complex 2, 54C THF * Complex 2+ * Complex 2+, 54C DMSO * Complex 2+, 54C THF * Complex 3 * Complex 3, 54C DMSO * Complex 3, 54C THF o Excel file: additive and thermolysis reaction standard initial concentrations Crystallography data: Crystallography data is contained in a master folder. In which are subfolders for the three reported structures. These subfolders each contain relevant data files needed to analyze the data and reported to the CCDC (cif, FCF, PCF, etc.) and also include the checkcif files. The cif files can be opened by any crystallographic software (e.g. Crystalmaker, Olex, etc.). Folder listing: * Crystallography Data * Complex 2 Pd PPh3 o Contains: check cif (PDF), cif, jpeg, fab, fcf, hkl, pcf, res, rich text format, abs, hkl and pfp files. * Complex 2+ Pd PPh3 SbF6 o Contains: check cif (PDF), cif, fdf, hkl, jpeg, pcf and rich text format files. * Complex 3 Pd dppe o Contains: check cif (PDF), cif, fcf, hkl, pcf, res and rich text format files. ChemDraws/Images: All ChemDraws, figures, schemes, etc are included as jpeg files. These files are separated into a folder for those corresponding to the manuscript main text and the supporting information. Folder listing (images saved as jpeg files): * Images o Main Body Images o Supplemental Information Images * Theory folder: * The theory folder is a master folder containing computational data from the Density functional theory (DFT) calculations. Within the theory folder are two sub-folders named "optimization" and "single_points." Both sub-folders contain raw output (".log") files prepared using the Gaussian 16 package. The ".log" files in the "optimization" sub-folder were prepared by performing geometry optimizations and frequency analysis on the structures shown in the paper and SI, while the".log" files in the "single_points" sub-folder were prepared by performing single point calculations on the same structures. All the files may be read as text by any word processing program, or viewed as image by any suitable viewing program such as Avogadro or Molden. Computational details are discussed in the "Computational Details" section of the SI. * Naming of files: The files in both sub-folders are named according to the following guidelines: * 1. Name of Figure/ Scheme in which the structure is presented. * 2. Ligand type present in the structure. * 3. The reaction step in which the structure is involved in the respective figure/ * scheme. This refers to the intermediate(s) going into each reaction step, or * products formed from the preceding step. * 4. In Figure 3, step 1a in all ligand systems refers to the transition state * structure for thermolysis . * 5. In Schemes S5-S7, presence/ absence of CO in the complexes is indicated. * 6. In Schemes S9-S14, the position of the structure is indicated using top, * down,left and right. * 7. Catalysts, substrates, ligands and other small molecules present in the reaction * pathways are named. * Files listing (all folders contain .log files): * +---Theory * +---optimization * | Acetonitrile.log * | Ag.log * | AgCl.log * | co.log * | Fig3_dppe_step1.log * | Fig3_dppe_step1a.log * | Fig3_dppe_step2.log * | Fig3_dppe_step3.log * | Fig3_dppe_step4.log * | Fig3_dppe_step5.log * | Fig3_dppe_step6.log * | Fig3_dppe_step7.log * | Fig3_dppe_step8.log * | Fig3_dppe_step9.log * | Fig3_PPh3_step1.log * | Fig3_PPh3_step1a.log * | Fig3_PPh3_step2.log * | Fig3_PPh3_step3.log * | Fig3_PPh3_step4.log * | Fig3_PPh3_step5.log * | Fig3_PPh3_step6.log * | Fig3_PPh3_step7.log * | Fig3_PPh3_step8.log * | Fig3_PPh3_step9.log * | Fig3_PtBu3_step7.log * | Fig3_PtBu3_step8.log * | Fig3_PtBu3_step9.log * | Fig3_PtBu3_stp1.log * | Fig3_PtBu3_stp1a.log * | Fig3_PtBu3_stp2.log * | Fig3_PtBu3_stp3.log * | Fig3_PtBu3_stp4.log * | Fig3_PtBu3_stp5.log * | Fig3_PtBu3_stp6.log * | Na.log * | NaCl.log * | SchemeS3_step1_catalyst.log * | SchemeS3_step1_substrate.log * | SchemeS3_step2.log * | SchemeS3_step3.log * | SchemeS3_step4.log * | SchemeS3_step5.log * | SchemeS4_step1_catalyst.log * | SchemeS4_step2.log * | SchemeS4_step2_ligand.log * | SchemeS4_step3.log * | SchemeS4_step4.log * | SchemeS4_step5.log * | SchemeS5_step7_noCO.log * | SchemeS6_step3.log * | SchemeS6_step7_withCO.log * | SchemeS7_step6_withCO.log * | SchemeS9_step2_left.log * | SchemeS10_step2_down.log * | SchemeS10_step2_left.log * | SchemeS10_step2_top.log * | SchemeS11_step2_left.log * | SchemeS12_step2_down_right.log * | SchemeS12_step2_left.log * | SchemeS12_step2_top_left.log * | SchemeS12_step2_top_right.log * | SchemeS13_step2_left.log * | SchemeS13_step2_top.log * | SchemeS14_step2_down.log * | SchemeS14_step2_left.log * | Styrene.log * | * \---single_points * Acetonitrile.log * Ag.log * AgCl.log * co.log * Fig3_dppe_step1.log * Fig3_dppe_step1a.log * Fig3_dppe_step2.log * Fig3_dppe_step3.log * Fig3_dppe_step4.log * Fig3_dppe_step5.log * Fig3_dppe_step6.log * Fig3_dppe_step7.log * Fig3_dppe_step8.log * Fig3_dppe_step9.log * Fig3_PPh3_step1.log * Fig3_PPh3_step1a.log * Fig3_PPh3_step2.log * Fig3_PPh3_step3.log * Fig3_PPh3_step4.log * Fig3_PPh3_step5.log * Fig3_PPh3_step6.log * Fig3_PPh3_step7.log * Fig3_PPh3_step8.log * Fig3_PPh3_step9.log * Fig3_PtBu3_step7.log * Fig3_PtBu3_step8.log * Fig3_PtBu3_step9.log * Fig3_PtBu3_stp1.log * Fig3_PtBu3_stp1a.log * Fig3_PtBu3_stp2.log * Fig3_PtBu3_stp3.log * Fig3_PtBu3_stp4.log * Fig3_PtBu3_stp5.log * Fig3_PtBu3_stp6.log * Na.log * NaCl.log * SchemeS3_step1_catalyst.log * SchemeS3_step1_substrate.log * SchemeS3_step2.log * SchemeS3_step3.log * SchemeS3_step4.log * SchemeS3_step5.log * SchemeS4_step1_catalyst.log * SchemeS4_step2.log * SchemeS4_step2_ligand.log * SchemeS4_step3.log * SchemeS4_step4.log * SchemeS4_step5.log * SchemeS5_step7_noCO.log * SchemeS6_step3.log * SchemeS6_step7_withCO.log * SchemeS7_step6_withCO.log * SchemeS9_step2_left.log * SchemeS10_step2_down.log * SchemeS10_step2_left.log * SchemeS10_step2_top.log * SchemeS11_step2_left.log * SchemeS12_step2_down_right.log * SchemeS12_step2_left.log * SchemeS12_step2_top_left.log * SchemeS12_step2_top_right.log * SchemeS13_step2_left.log * SchemeS13_step2_top.log * SchemeS14_step2_down.log * SchemeS14_step2_left.log * Styrene.log Relationship between files: None Additional related data collected that was not included in the current data package: None Are there multiple versions of the dataset? N -------------------------- METHODOLOGICAL INFORMATION -------------------------- Description of methods used for collection, generation, and processing of data: Documentation for the synthesis and instrumentation used for the characterization of the reported compounds is located within the supplementary information. People involved with sample collection, processing, analysis and/or submission: Tedd Wiessner synthesized and performed all NMR characterization of the reported compounds. Performed all experimental reactivity studies. Samuel Fosu and Riffat Parveen performed all computations for theoretical work. Nigam Rath collected and solved all crystallographic data.