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

The complexes [RuCp(8MTT-kappa S)LL'] and [RuCp(8MTT-kappa N7)LL'] (8MTT = 8-methylthio-theophyllinate; L, L' = PTA, mPTA; L = mPTA, L' = PPh3; PTA = 1,3,5-triaza-7-phosphaadamantane, mPTA = N-methyl-1,3,5triaza-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-kappa S)(PTA)(2)] and [RuCp(8MTT-kappa S)(mPTA)(PPh3)](+) are slightly stabilized by favourable Gibbs free energy respect to [RuCp(8MTT-kappa N7) (PTA)(2)] and [RuCp(8MTT-kappa N7)(mPTA)(PFh(3))](+) in gas phase while in water and ethanol the calculated Gibbs free energy showed that the 8MTT-kappa S-complexes are quite more stable than the corresponding 8MTT-kappa N7-complexes. However, the [RuCp(8MTT-kappa N7)(mPTA)(2)](2+) is more stable than the corresponding kappa S-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-kappa S-complexes, [RuCp(8MTT-kappa S) (mPTA)(PPh3)](CF3OSO2) (1) and [RuCp(8MTT-kappa S)(mPTA)(2)]Cl(CF3OSO2)center dot 1.5H(2)O (2.1.5H(2)O) were synthesized and characterized by single crystal X-ray diffraction. (C) 2016 Elsevier B.V. All rights reserved.