{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Lentz N"],"funding":["Swiss National Science Foundation"],"pagination":["e202202672"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10092520"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["28(68)"],"pubmed_abstract":["Ligand design is crucial for the development of new catalysts and materials with new properties. Herein, the synthesis and unique hemilabile coordination properties of new bis-pyridylidene amine (bis-PYE) ligands to palladium, and preliminary catalytic activity of these complexes in formic acid dehydrogenation are described. The synthetic pathway to form cationic complexes [Pd(bis-PYE)Cl(L)]X with a cis-coordinated N,N-bidentate bis-PYE ligand is flexible and provides access to a diversity of Pd<sup>II</sup> complexes with different ancillary ligands (L=pyridine, DMAP, PPh<sub>3</sub> , Cl, P(OMe)<sub>3</sub> ). The <sup>1</sup> H NMR chemical shift of the trans-positioned PYE N-CH<sub>3</sub> unit is identified as a convenient and diagnostic handle to probe the donor properties of these ancillary ligands and demonstrates the electronic flexibility of the PYE ligand sites. In the presence of a base, the originally cis-coordinated bis-PYE ligand adopts a N,N,N-tridentate coordination mode with the two PYE units in mutual trans position. This cis-trans isomerization is reverted in presence of an acid, demonstrating a unique structural and steric flexibility of the bis-PYE ligand at palladium in addition to its electronic adaptability. The palladium complexes are active in formic acid dehydrogenation to H<sub>2</sub> and CO<sub>2</sub> . The catalytic performance is directly dependent on the ligand bonding mode, the nature of the ancillary ligand, the counteranion, and additives. The most active system features a bidentate bis-PYE ligand, PPh<sub>3</sub> as ancillary ligand and accomplishes turnover frequencies up to 525 h<sup>-1</sup> in the first hour and turnover numbers of nearly 1000, which is the highest activity reported for palladium-based catalysts to date."],"journal":["Chemistry (Weinheim an der Bergstrasse, Germany)"],"pubmed_title":["Sterically and Electronically Flexible Pyridylidene Amine Dinitrogen Ligands at Palladium: Hemilabile cis/trans Coordination and Application in Dehydrogenation Catalysis."],"pmcid":["PMC10092520"],"funding_grant_id":["200020","200020_182663"],"pubmed_authors":["Streit Y","Knorr P","Albrecht M","Lentz N"],"additional_accession":[]},"is_claimable":false,"name":"Sterically and Electronically Flexible Pyridylidene Amine Dinitrogen Ligands at Palladium: Hemilabile cis/trans Coordination and Application in Dehydrogenation Catalysis.","description":"Ligand design is crucial for the development of new catalysts and materials with new properties. Herein, the synthesis and unique hemilabile coordination properties of new bis-pyridylidene amine (bis-PYE) ligands to palladium, and preliminary catalytic activity of these complexes in formic acid dehydrogenation are described. The synthetic pathway to form cationic complexes [Pd(bis-PYE)Cl(L)]X with a cis-coordinated N,N-bidentate bis-PYE ligand is flexible and provides access to a diversity of Pd<sup>II</sup> complexes with different ancillary ligands (L=pyridine, DMAP, PPh<sub>3</sub> , Cl, P(OMe)<sub>3</sub> ). The <sup>1</sup> H NMR chemical shift of the trans-positioned PYE N-CH<sub>3</sub> unit is identified as a convenient and diagnostic handle to probe the donor properties of these ancillary ligands and demonstrates the electronic flexibility of the PYE ligand sites. In the presence of a base, the originally cis-coordinated bis-PYE ligand adopts a N,N,N-tridentate coordination mode with the two PYE units in mutual trans position. This cis-trans isomerization is reverted in presence of an acid, demonstrating a unique structural and steric flexibility of the bis-PYE ligand at palladium in addition to its electronic adaptability. The palladium complexes are active in formic acid dehydrogenation to H<sub>2</sub> and CO<sub>2</sub> . The catalytic performance is directly dependent on the ligand bonding mode, the nature of the ancillary ligand, the counteranion, and additives. The most active system features a bidentate bis-PYE ligand, PPh<sub>3</sub> as ancillary ligand and accomplishes turnover frequencies up to 525 h<sup>-1</sup> in the first hour and turnover numbers of nearly 1000, which is the highest activity reported for palladium-based catalysts to date.","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Dec","modification":"2024-11-10T07:46:30.441Z","creation":"2024-11-10T07:46:30.441Z"},"accession":"S-EPMC10092520","cross_references":{"pubmed":["36066486"],"doi":["10.1002/chem.202202672"]}}