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and trans are not well defined for\nmonophosphine\nPd(II) complexes. In this article, cis and trans refer to the relationship of CF3 and Ph (see Figure 4)."},{"key":"ref23\/cit23","doi-asserted-by":"publisher","DOI":"10.1021\/ja0602389"},{"key":"ref24\/cit24","unstructured":"Deposition\nnumbers 2172315 (for cis-2), and 2172314 (for cis-3) contain the supplementary crystallographic\ndata for this paper. These data are provided free of charge by the\njoint Cambridge Crystallographic Data Centre and Fachinformationszentrum\nKarlsruhe Access Structures service."},{"key":"ref25\/cit25a","doi-asserted-by":"publisher","DOI":"10.1021\/ja00120a012"},{"key":"ref25\/cit25b","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200900373"},{"key":"ref26\/cit26a","doi-asserted-by":"publisher","DOI":"10.1021\/ja0635736"},{"key":"ref26\/cit26b","doi-asserted-by":"publisher","DOI":"10.1021\/om0001265"},{"key":"ref27\/cit27","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2099"},{"key":"ref28\/cit28","unstructured":"Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision D.01; Gaussian, Inc.: Wallingford CT, 2013."},{"key":"ref29\/cit29","doi-asserted-by":"publisher","DOI":"10.1021\/cr941141k"},{"key":"ref30\/cit30","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201808229"},{"key":"ref31\/cit31","unstructured":"Since the total energy is kept\nconstant under NVE (microcanonical) conditions, this might not be\nappropriate to represent experimental conditions under which only\nthe kinetic energy (not the potential energy) remains constant. While\nan NPT ensemble would best represent experimental conditions (requires\nuse of a barostat, which is not easily available), the NVT (canonical)\nensemble is a good approximation assuming there are only negligible\nchanges in solvent density and therefore constant pressure equals\nconstant volume. Calculations of an NVT ensemble require a thermostat,\nwhich is available in both xTB and ORCA software."},{"key":"ref32\/cit32","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1606"},{"key":"ref33\/cit33","doi-asserted-by":"publisher","DOI":"10.1021\/ic500284q"},{"key":"ref34\/cit34","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00163"},{"key":"ref35\/cit35","doi-asserted-by":"publisher","DOI":"10.1021\/ja801362e"},{"key":"ref36\/cit36","unstructured":"The variation\nof the overall\nactivation free energy barrier to reach TSTM was less pronounced however\n(when the ligand dissociation energy was larger, smaller subsequent\nactivation barriers were calculated and vice-versa, see SI for further\ninformation)."},{"key":"ref37\/cit37a","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1244"},{"key":"ref37\/cit37b","doi-asserted-by":"publisher","DOI":"10.1055\/s-0031-1290564"},{"key":"ref37\/cit37c","doi-asserted-by":"publisher","DOI":"10.1039\/c2sc20331f"},{"key":"ref38\/cit38a","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.8b01176"},{"key":"ref38\/cit38b","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.7b00118"},{"key":"ref39\/cit39","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c05293"},{"key":"ref40\/cit40a","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20020301)8:53.0.CO;2-M"},{"key":"ref40\/cit40b","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19980420)37:7<994::AID-ANIE994>3.0.CO;2-H"},{"key":"ref41\/cit41","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990802)38:15<2252::AID-ANIE2252>3.0.CO;2-Z"},{"key":"ref42\/cit42a","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.201800015"},{"key":"ref42\/cit42b","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201507356"},{"key":"ref42\/cit42c","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201406505"},{"key":"ref44\/cit44","unstructured":"Our xTB single\npoint\nenergy calculations of the same stationary points indicated that xTB\nenergetically follows the same pathway preference as DFT in favoring\nthe ionic pathway in polar solvent via fluoride abstraction and CF3 anion rebound. By contrast, for the difluorocarbene releasing\npathway (as found to be favored in non-polar medium by DFT), xTB energies\nsuggest different selectivities of the mechanistic pathways. xTB-based\ndifluorocarbene post-transition state dynamics are hence not applicable."},{"key":"ref45\/cit45","unstructured":"To comment on the energy\ndifferences of the various possibilities we speculate the following:\nThe pentacoordinate intermediates change their conformation via a\nBerry-type pseudorotation mechanism. Due to steric effects the trigonal\nbipyramids (e.g. III) are energetically favored, whereas square pyramids\n(e.g. II) are higher in energy. Moreover, the axial positions in the\ntrigonal bipyramid experience increased steric repulsion due to three\nangles of 90\u00b0 to their nearest neighbors and only one ligand\nbeing located further away at 180\u00b0. The equatorial positions\nare sterically less encumbered (only two 90\u00b0 angles and two 120\u00b0\nangles). As a result, the large phosphine ligands appear to preferentially\norient themselves in the equatorial positions (e.g. in III). Directly\ncomparing the two transition states where solvent (MeCN) dissociates,\nthe two phosphines are axial en route to trans-2 (i.e. more steric repulsion and hence higher in energy),\nwhereas the phosphines are equatorial en route to cis-2 (i.e. experiencing less steric repulsion)."},{"key":"ref46\/cit46a","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"ref46\/cit46b","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"ref47\/cit47","doi-asserted-by":"publisher","DOI":"10.1063\/1.444267"},{"key":"ref48\/cit48","doi-asserted-by":"publisher","DOI":"10.1007\/BF01114537"},{"key":"ref49\/cit49","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344"},{"key":"ref50\/cit50","doi-asserted-by":"publisher","DOI":"10.1063\/1.2370993"},{"key":"ref51\/cit51","doi-asserted-by":"publisher","DOI":"10.1039\/b508541a"},{"key":"ref52\/cit52","doi-asserted-by":"publisher","DOI":"10.1021\/jp810292n"}],"container-title":["JACS Au"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacsau.3c00724","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacsau.3c00724","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,1,22]],"date-time":"2024-01-22T09:12:51Z","timestamp":1705914771000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/jacsau.3c00724"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,12,29]]},"references-count":103,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2024,1,22]]}},"alternative-id":["10.1021\/jacsau.3c00724"],"URL":"https:\/\/doi.org\/10.1021\/jacsau.3c00724","relation":{},"ISSN":["2691-3704","2691-3704"],"issn-type":[{"value":"2691-3704","type":"print"},{"value":"2691-3704","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,12,29]]}}}