{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T18:09:21Z","timestamp":1782929361999,"version":"3.54.5"},"reference-count":81,"publisher":"Royal Society of Chemistry (RSC)","issue":"24","license":[{"start":{"date-parts":[[2025,10,30]],"date-time":"2025-10-30T00:00:00Z","timestamp":1761782400000},"content-version":"vor","delay-in-days":302,"URL":"http:\/\/creativecommons.org\/licenses\/by\/3.0\/"}],"funder":[{"DOI":"10.13039\/501100001711","name":"Schweizerischer Nationalfonds zur F\u00f6rderung der Wissenschaftlichen Forschung","doi-asserted-by":"publisher","award":["200020_212863"],"award-info":[{"award-number":["200020_212863"]}],"id":[{"id":"10.13039\/501100001711","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["rsc.org"],"crossmark-restriction":true},"short-container-title":["Catal. Sci. Technol."],"abstract":"<jats:p>\n                    Palladium complexes with symmetric\n                    <jats:italic>N<\/jats:italic>\n                    ,\n                    <jats:italic>N<\/jats:italic>\n                    -bidentate bis(pyridinium amidate) ligands catalyze the olefin polymerization already at mild conditions, when the pyridinium site is\n                    <jats:italic>ortho<\/jats:italic>\n                    ,\n                    <jats:italic>ortho<\/jats:italic>\n                    -dimethylated. The carbonyl groups engage in metal coordination.\n                  <\/jats:p>","DOI":"10.1039\/d5cy01102g","type":"journal-article","created":{"date-parts":[[2025,10,30]],"date-time":"2025-10-30T09:20:46Z","timestamp":1761816046000},"page":"7464-7472","update-policy":"https:\/\/doi.org\/10.1039\/rsc_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Tunable bis(pyridinium amidate) ligands efficiently promote palladium-catalyzed ethylene polymerization"],"prefix":"10.1039","volume":"15","author":[{"given":"Esa\u00efe","family":"Reusser","sequence":"first","affiliation":[{"name":"Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7403-2329","authenticated-orcid":false,"given":"Martin","family":"Albrecht","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"292","published-online":{"date-parts":[[2025]]},"reference":[{"key":"D5CY01102G\/cit1\/1","doi-asserted-by":"crossref","first-page":"6414","DOI":"10.1021\/ja00128a054","volume":"117","author":"Johnson","year":"1995","journal-title":"J. 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J."},{"key":"D5CY01102G\/cit28\/1","unstructured":"Quantitative  19 F NMR analysis (see ref. 29) revealed the presence of 0.75 eq. PF 6  per ligand in 2a and 0.25 eq. PF 6  for 2c"},{"key":"D5CY01102G\/cit29\/1","unstructured":"Quantitative  19 F NMR analysis was performed by adding a drop of 1,2,4,5-tetrafluorobenzene to a pure solution of the analyte. Subsequent comparison of the standard\/analyte ratio in  1 H and  19 F NMR spectra indicated the number of PF 6  anions per ligand unit. The method was tested against control samples with known number of fluorine nuclei and gave results within classical NMR integration errors. 16 scans and a relaxation delay of 6 s were used to ensure a reliable signal integration (Fig. S1,S2)"},{"key":"D5CY01102G\/cit30\/1","unstructured":"Upon exposing 2c to 2.5 eq. LiHMDS, a species spectroscopically different from 3c was isolated. The chemical shift for the NCH 3  resonance of this species, \u03b4 H  = 3.86 lies between the values observed for 2c (\u03b4 H  = 4.20) and 3c (\u03b4 H  = 3.72, Fig. S17). Additionally, CHN elemental analysis suggested a composition consistent with 3c + LiPF 6  + H 2 O, while mass spectrometry detected M+Li signals but showed no signal corresponding to M+H (Fig. S18). Quantitative  19 F analysis (see ref. 29) indicated 0.9 eq. PF 6  per ligand. Similar data were obtained from the reaction of 2a and 2d with LiHMDS after washing the product with THF, suggesting formation of a LiPF 6  adduct analogous to that observed for 2c"},{"key":"D5CY01102G\/cit31\/1","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1021\/ja953247i","volume":"118","author":"Johnson","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"D5CY01102G\/cit32\/1","doi-asserted-by":"crossref","first-page":"2354","DOI":"10.1039\/C9PY00226J","volume":"10","author":"Wang","year":"2019","journal-title":"Polym. 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Chem."},{"key":"D5CY01102G\/cit37\/1","unstructured":"Complex 4d displayed two sets of signals even in the presence of excess chloride, most distinctly revealed by the two sets of two different resonances each for the NCH 3  and C pyr \u2013CH 3  groups (Fig. S36). These sets were attributed to syn and anti isomers due to hindered rotation about the exocyclic N PYA \u2013C pyr  bond. Upon heating complex 4d to 55 \u00b0C in DMSO, one exchange becomes fast on the NMR time scale (attributed to the solvento\/chlorido exchange), and at 75 \u00b0C, the two remaining sets of signals attributed to the syn\/anti rotamers also coalesced (Fig. S35). The energy barrier for this second process was estimated using the Eyring equation (ref 38,39) at \u0394G \u2021  = 17.9 kcal mol \u22121 . Notably, in D 2 O, only two sets of signals were distinguishable, which was attributed to the rotamers in approximate 3:1 ratio and the absence of the solvento complex (Fig. S37). In both solvents, only the C pyr \u2013CH 3  chemical shifts were sufficiently different, which prevented a full assignment of syn vs anti isomers"},{"key":"D5CY01102G\/cit38\/1","doi-asserted-by":"crossref","first-page":"285","DOI":"10.1021\/jo201890f","volume":"77","author":"Chen","year":"2012","journal-title":"J. Org. Chem."},{"key":"D5CY01102G\/cit39\/1","doi-asserted-by":"crossref","first-page":"1425","DOI":"10.1021\/acs.jchemed.0c00057","volume":"97","author":"Huggins","year":"2020","journal-title":"J. Chem. 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Soc."},{"key":"D5CY01102G\/cit66\/1","unstructured":"While this elongation of the K\u2026F interactions might point to partial localization of negative charge on the bis(amide) oxygen atoms, the C=O bonds in 6d are in the 1.226(4)\u20131.238(7) \u00c5 range and thus identical within esds to those of ligand precursor 2d (C=O 1.220(7) \u00c5) without any alkali metal coordination"},{"key":"D5CY01102G\/cit67\/1","doi-asserted-by":"crossref","first-page":"809","DOI":"10.1016\/j.jfluchem.2006.02.018","volume":"127","author":"He","year":"2006","journal-title":"J. Fluorine Chem."},{"key":"D5CY01102G\/cit68\/1","doi-asserted-by":"crossref","first-page":"8766","DOI":"10.1021\/ac202287y","volume":"83","author":"Do","year":"2011","journal-title":"Anal. Chem."},{"key":"D5CY01102G\/cit69\/1","doi-asserted-by":"crossref","first-page":"e21422","DOI":"10.1002\/cmr.a.21422","volume":"45A","author":"Mattes","year":"2016","journal-title":"Concepts Magn. 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