Enhanced ?-back-donation resulting in the trans labilization of a pyridine ligand in an N-heterocyclic carbene (NHC) PdII precatalyst: a case study

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dc.authoridÖzdemir, İsmail/0000-0001-6325-0216
dc.authoridKARABIYIK, HANDE/0000-0001-6180-2080
dc.authorwosidÖzdemir, İsmail/ABI-5192-2020
dc.authorwosidKARABIYIK, HANDE/O-9745-2019
dc.contributor.authorKarabiyik, Hande
dc.contributor.authorYigit, Beyhan
dc.contributor.authorYigit, Murat
dc.contributor.authorOzdemir, Ismail
dc.contributor.authorKarabiyik, Hasan
dc.date.accessioned2024-08-04T20:46:02Z
dc.date.available2024-08-04T20:46:02Z
dc.date.issued2019
dc.departmentİnönü Üniversitesien_US
dc.description.abstractThe molecular structure of the benzimidazol-2-ylidene-PdCl2-pyridine-type PEPPSI (pyridine-enhanced precatalyst, preparation, stabilization and initiation) complex {1,3-bis[2-(diisopropylamino) ethyl] benzimidazol-2-ylidene-kappa C-2}dichlorido(pyridine-kappa N) palladium(II), [PdCl2(C5H5N)(C23H40N4)], has been characterized by elemental analysis, IR and NMR spectroscopy, and natural bond orbital (NBO) and charge decomposition analysis (CDA). Cambridge Structural Database (CSD) searches were used to understand the structural characteristics of the PEPPSI complexes in comparison with the usual Nheterocyclic carbene (NHC) complexes. The presence of weak C-H center dot center dot center dot Cl-type hydrogen-bond and pi-pi stacking interactions between benzene rings were verified using NCI plots and Hirshfeld surface analysis. The preferred method in the CDA of PEPPSI complexes is to separate their geometries into only two fragments, i. e. the bulky NHC ligand and the remaining fragment. In this study, the geometry of the PEPPSI complex is separated into five fragments, namely benzimidazol-2-ylidene (Bimy), two chlorides, pyridine (Py) and the Pd II ion. Thus, the individual roles of the Pd atom and the Py ligand in the donation and back-donation mechanisms have been clearly revealed. The NHC ligand in the PEPPSI complex in this study acts as a strong pi-donor with a considerable amount of pi-back-donation from Pd to Ccarbene. The electron-poor character of Pd II is supported by pi-back-donation from the Pd centre and the weakness of the Pd-N(Py) bond. According to CSD searches, Bimy ligands in PEPPSI complexes have a stronger pi-donating ability than imidazol-2-ylidene ligands in PEPPSI complexes.en_US
dc.description.sponsorshipDokuz Eylul University [KB.FEN.13]en_US
dc.description.sponsorshipFunding for this research was provided by: Dokuz Eylul University (grant No. 2010.KB.FEN.13).en_US
dc.identifier.doi10.1107/S2053229619007745
dc.identifier.endpage+en_US
dc.identifier.issn2053-2296
dc.identifier.pmid31271383en_US
dc.identifier.scopus2-s2.0-85068608904en_US
dc.identifier.scopusqualityQ3en_US
dc.identifier.startpage941en_US
dc.identifier.urihttps://doi.org/10.1107/S2053229619007745
dc.identifier.urihttps://hdl.handle.net/11616/98860
dc.identifier.volume75en_US
dc.identifier.wosWOS:000474222100015en_US
dc.identifier.wosqualityQ3en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.indekslendigikaynakPubMeden_US
dc.language.isoenen_US
dc.publisherInt Union Crystallographyen_US
dc.relation.ispartofActa Crystallographica Section C-Structural Chemistryen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectN-heterocyclic carbeneen_US
dc.subjectNHCen_US
dc.subjectCSDen_US
dc.subjectcharge decomposition anaylsesen_US
dc.subjectCDAen_US
dc.subjecttrans influenceen_US
dc.subjectback-donationen_US
dc.subjectPEPPSIen_US
dc.subjectcrystal structureen_US
dc.subjectquantum chemical calculationsen_US
dc.titleEnhanced ?-back-donation resulting in the trans labilization of a pyridine ligand in an N-heterocyclic carbene (NHC) PdII precatalyst: a case studyen_US
dc.typeArticleen_US

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