Synthesis and structural evaluation of organo-ruthenium complexes with ß-diketonates

Uršič, Matija (author), Lipec, Tanja (author), Meden, Anton (author), Turel, Iztok (author)

Four novel ruthenium organometallic complexes: [(η$^6$-p-cymene)Ru(4,4,4-trifluoro-1-(4-bromophenyl)-1,3-butanedione)Cl] (1), [(η$^6$-p-cymene)Ru(4,4,4-trifluoro-1-(4-bromophenyl)-1,3-butanedione)pta]PF$_6$ (2), [(η$^6$-p-cymene)Ru(4,4,4-trifluoro-1-(4-iodophenyl)-1,3-butanedione)Cl] (3) and [(η$^6$-p-cymene)Ru(4,4,4-trifluoro-1-(4-iodophenyl)-1,3-butanedione)pta]PF$_6$ (4) were synthesized and characterized by elemental analysis, infrared (IR), UV-Vis, NMR and mass spectroscopy and single-crystal X-ray diffraction. The crystal structures and spectroscopic data were compared to the previously published complexes [(η$^6$-p-cymene)Ru(4,4,4-trifluoro-1-(4-chloro-phenyl)-1,3-butanedione)Cl] (5) and [(η$^6$-p-cymene)Ru(4,4,4-trifluoro-1-(4-chlorophenyl)-1,3-butanedione)pta]PF$_6$ (6). The pairs of complexes 1 and 3 as well as 2 and 4 are isostructural, with the former crystallizing in triclinic P-1 and the latter in monoclinic P2$_1$/c. The ruthenium(II) ion is found in a pseudo-octahedral “piano-stool” geometry in all compounds. Bond lengths and angles are consistent with other complexes of this type. Complexes 2 and 4 exhibit some moderate dynamic disorder. The lack of hydrogen bonding and major π-π interactions means that most of intramolecular interactions are fairly weak and involve halogen atoms present. This was further confirmed by $^1$H-NMR spectra, where a significant difference is observed only on the ligand near the halogen atom, following an expected trend. The combined data show that the difference in any activity depends substantially on the type of the ligand′s substituted halogen atom.

• Language: English
• Keywords: organoruthenium complexes, ß-diketonate ligands, halogen substituents, 1, 3, 5-triazaphosphoadamantane (pta) ligand, disorder
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2017
• Number of pages: 12 str.
• Numbering: Vol. 22, iss. 2, art. 326
• PID: 20.500.12556/RUL-131179
• UDC: 546.96:547-316
• ISSN on article: 1420-3049
• DOI: 10.3390/molecules22020326
• COBISS.SI-ID: 1537371075
• Publication date in RUL: 23.09.2021

Record is a part of a journal

• Title: Molecules
• Shortened title: Molecules
• Publisher: MDPI
• ISSN: 1420-3049
• COBISS.SI-ID: 18462981

Licences

• License: CC BY 4.0, Creative Commons Attribution 4.0 International
• Link: http://creativecommons.org/licenses/by/4.0/
• Description: This is the standard Creative Commons license that gives others maximum freedom to do what they want with the work as long as they credit the author.
• Licensing start date: 20.02.2017

Secondary language

• Language: Slovenian
• Keywords: organorutenijevi kompleksi, ß-diketonatni ligandi, halogenski substituenti, 1, 3, 5-triazafosfoadamantan (pta) ligand, nered

Projects

• Funder: ARRS - Slovenian Research Agency
• Funding programme: Junior Researcher Grant

• Funder: ARRS - Slovenian Research Agency
• Project number: P1-0175
• Name: Sinteza, struktura, lastnosti snovi in materialov