title: Synthesis and Structural Evaluation of Organo-Ruthenium Complexes with β-Diketonates.
abstract: Four novel ruthenium organometallic complexes: [(η⁶-p-cymene)Ru(4,4,4-trifluoro-1-(4-bromophenyl)-1,3-butanedione)Cl] (1), [(η⁶-p-cymene)Ru(4,4,4-trifluoro-1-(4-bromophenyl)-1,3-butanedione)pta]PF₆ (2), [(η⁶-p-cymene)Ru(4,4,4-trifluoro-1-(4-iodophenyl)-1,3-butanedione)Cl] (3) and [(η⁶-p-cymene)Ru(4,4,4-trifluoro-1-(4-iodophenyl)-1,3-butanedione)pta]PF₆ (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 [(η⁶-p-cymene)Ru(4,4,4-trifluoro-1-(4-chloro-phenyl)-1,3-butanedione)Cl] (5) and [(η⁶-p-cymene)Ru(4,4,4-trifluoro-1-(4-chlorophenyl)-1,3-butanedione)pta]PF₆ (6). The pairs of complexes1and3as well as2and4are isostructural, with the former crystallizing in triclinic P-1 and the latter in monoclinic P2₁/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. Complexes2and4exhibit 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 ¹H-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.
authors.affiliation: Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1001 Ljubljana, Slovenia. matija.ursic@fkkt.uni-lj.si.
authors.forename: Matija
authors.initials: M
authors.lastname: Uršič
authors.affiliation: Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1001 Ljubljana, Slovenia. tanja90@gmail.com.
authors.forename: Tanja
authors.initials: T
authors.lastname: Lipec
authors.affiliation: Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1001 Ljubljana, Slovenia. Anton.Meden@fkkt.uni-lj.si.
authors.forename: Anton
authors.initials: A
authors.lastname: Meden
authors.affiliation: Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1001 Ljubljana, Slovenia. iztok.turel@fkkt.uni-lj.si.
authors.forename: Iztok
authors.initials: I
authors.lastname: Turel
mesh_terms: D018360:Crystallography, X-Ray; D006219:Halogens / Q000737:chemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009930:Organic Chemicals / Q000138:chemical synthesis / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D006219:Halogens; D008024:Ligands; D009930:Organic Chemicals; D012428:Ruthenium
keywords: 1,3,5-triazaphosphoadamantane (pta) ligand; disorder; halogen substituents; organoruthenium complexes; β-diketonate ligands