Synthesis, characterization, X-ray structural determination and theoretical study of the complexes [RuCp(8MTT-κS)LL′] (8MTT=8-methylthio-theophyllinate; L,L′=PTA, mPTA; L=mPTA, L′=PPh3; PTA=1,3,5-triaza-7-phosphaadamantane, mPTA=N-methyl-1,3,5-triaza-7-phosphaadamantane)

• Published in: Inorganica Chimica Acta Vol. 455; pp. 557 - 567
• Main Authors: Hajji, Lazhar, Jara-Pérez, Vicente, Saraiba-Bello, Cristobal, Segovia-Torrente, Gaspar, Serrano-Ruiz, Manuel, Romerosa, Antonio
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 30.01.2017; Elsevier Science Ltd
• Subjects: Chemical synthesis; DFT; Ethanol; Free energy; Gibbs free energy; Infrared spectra; PTA derivatives; Ruthenium; Single crystals; Structural analysis; Theoretical studies; Thermodynamics; Thio-purines; Water soluble complexes; X-ray diffraction; Water soluble complexes; Thio-purines; Ruthenium; DFT; Theoretical studies; PTA derivatives
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2016.05.048

Two new thiopurine-κS-complexes, [RuCp(8MTT-κS)(mPTA)(PPh3)]+ (1) and [RuCp(8MTT-κS)(mPTA)2]2+ (2) were synthesized and characterized by single crystal X-ray diffraction. The thiopurine coordination was evaluated by DFT theoretical methods by study of the isomer complexes in gas phase and water. [Display omitted] •Synthesis of tow new examples of Ru-metal-κS-coordination-thioethers.•Water soluble ruthenium complexes with PTA and thiopurines.•Theoretical evaluation of κS- and κN-thioether coordination.•Stability of κS-thioether coordination larger than κN-thioether coordination in protic solvents.•The IR is not useful for determining κS- and κN-thioether coordination in {CpRu(L)(L′)} units. The complexes [RuCp(8MTT-κS)LL′] and [RuCp(8MTT-κN7)LL′] (8MTT=8-methylthio-theophyllinate; L,L′=PTA, mPTA; L=mPTA, L′=PPh3; PTA=1,3,5-triaza-7-phosphaadamantane, mPTA=N-methyl-1,3,5-triaza-7-phosphaadamantane) have been investigated by DFT theoretical methods. Structures, infrared spectra and thermodynamical properties in gas phase, water and ethanol of the studied complexes have been determined at B3LYP/DZVP level of theory. Complexes [RuCp(8MTT-κS)(PTA)2] and [RuCp(8MTT-κS)(mPTA)(PPh3)]+ are slightly stabilized by favourable Gibbs free energy respect to [RuCp(8MTT-κN7)(PTA)2] and [RuCp(8MTT-κN7)(mPTA)(PPh3)]+ in gas phase while in water and ethanol the calculated Gibbs free energy showed that the 8MTT-κS-complexes are quite more stable than the corresponding 8MTT-κN7-complexes. However, the [RuCp(8MTT-κN7)(mPTA)2]2+ is more stable than the corresponding κS-complex in gas phase while in water remains less stable. These theoretical results are in agreement with obtained until now experimental results as two new 8MTT-κS-complexes, [RuCp(8MTT-κS)(mPTA)(PPh3)](CF3OSO2) (1) and [RuCp(8MTT-κS)(mPTA)2]Cl(CF3OSO2)·1.5H2O (2·1.5H2O) were synthesized and characterized by single crystal X-ray diffraction.