Zvirzdinaite, Maryte, Garbe, Simon, Arefyeva, Natalia, Krause, Maren, von der Stueck, Rene and Klein, Axel ORCID: 0000-0003-0093-9619 (2017). Palladium(II) Complexes of Ambidentate and Potentially Cyclometalating 5-Aryl-3-(2 '-pyridyl)-1,2,4-triazine Ligands. Eur. J. Inorg. Chem. (13). S. 2011 - 2023. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1099-0682

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Abstract

The 5-aryl-3-(2'-pyridiyl)-1,2,4-triazine ligands under study [5-phenyl-(PyTZPh) L-1; 5-(3-methoxyphenyl)-(PyTZ3Me-OPh) L-2; 5-(4-methoxyphenyl)-(PyTZ4MeOPh) L-3; 5-(4-trifluoromethylphenyl)-(PyTZ4CF(3)Ph) L-4; 5-(4-fluorophenyl)-(PyTZ4FPh) L-5; and tris-3,5,6-(2'-pyridyl)-1,2,4-triazine (Py(3)TZ) L-6] react with [(COD) PdCl2] (COD = 1,5-cyclooctadiene) to form complexes [(L1-6) PdCl2] with N,N bidentate binding ligands, also including the potentially N,N,N tridentate ligand L-6. This was concluded from an in-depth NMR spectroscopic study of the new complexes and from comparison with Pd-terpy complexes [(R' terpy)PdCl]Cl [R'terpy = 4'-R'-2,2': 6',2 ''-terpyridine; R' = H or SMe], showing definite tridentate N,N,N coordination, and with the Pd-bpy complexes [(bpy)Pd(Mes)Cl] and [(bpy)PdCl2], showing definite bidentate N,N binding. The new ligands and complexes were fully characterised by multinuclear NMR spectroscopy, IR spectroscopy and mass spectrometry. No evidence for the parent triazine complexes is observed in EI-MS; instead, cyclometalated complexes (HCl elimination) were detected in all cases. TDA/TG experiments support this assumption. Attempts to prepare the cyclometalated derivatives as substances failed, in line with the unfavourable binding mode. Detailed electrochemical measurements reveal ligand-centred reductions at very moderate potentials, in line with UV/Vis absorption spectroscopy and DFT calculations, revealing very low-lying triazine-centred LUMOs. Results from cyclic voltammetry also support the composition of [(Py(3)TZ)PdCl2].

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Zvirzdinaite, MaryteUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Garbe, SimonUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Arefyeva, NataliaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Krause, MarenUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
von der Stueck, ReneUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Klein, AxelUNSPECIFIEDorcid.org/0000-0003-0093-9619UNSPECIFIED
URN: urn:nbn:de:hbz:38-234155
DOI: 10.1002/ejic.201601530
Journal or Publication Title: Eur. J. Inorg. Chem.
Number: 13
Page Range: S. 2011 - 2023
Date: 2017
Publisher: WILEY-V C H VERLAG GMBH
Place of Publication: WEINHEIM
ISSN: 1099-0682
Language: English
Faculty: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
DONOR CARRIER LIGANDS; X-RAY; DFT CALCULATIONS; SPECTROSCOPIC CHARACTERIZATION; CRYSTAL-STRUCTURES; PLATINUM(II) COMPLEXES; ANTICANCER ACTIVITY; BSA-BINDING; DNA-BINDING; L=5,6-DIPHENYL-3-(2-PYRIDYL)-1,2,4-TRIAZINE DPPTMultiple languages
Chemistry, Inorganic & NuclearMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/23415

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