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)

Abstract

Two new thiopurine-kS-complexes, [RuCp(8MTT-kS)(mPTA)(PPh3)] + (1) and [RuCp(8MTT-kS)(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.

Ruthenium complexes containing mPTA and thiopurines bis(8-thiotheophylline)-(CH2)n (n = 1 – 3; mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane)

“…The theoretical study showed that in gas phase the kS-complexes containing PTA and mPTA display similar stability, being those of mPTA somewhat larger than those with PTA (S14, SI). and those found in parent calculated complexes [21]. The calculated structures for 1, 2 and 3 kS-complexes are in agreement with the X-ray structures of [RuCp(8MTT-kS)(mPTA)2]Cl(CF3SO3) [21] although optimized Ru-P and Ru-S bond lengths are larger than crystalline ones.…”

“…and those found in parent calculated complexes [21]. The calculated structures for 1, 2 and 3 kS-complexes are in agreement with the X-ray structures of [RuCp(8MTT-kS)(mPTA)2]Cl(CF3SO3) [21] although optimized Ru-P and Ru-S bond lengths are larger than crystalline ones. Similar deviations were found in bibliography for Ru(II)complex structures when calculated at B3LYP/DZVP and B3LYP/LANL2DZ levels [22].…”