Bambusuril macrocycles have high affinity towards anions (X-) such as PF6- and SbF6- or BF4- and ClO4-. Therefore, addition of bambusurils to reaction mixtures containing these anions effectively removes the free anions from the reaction process. Hence, comparing reactions with and without addition of bambusurils can demonstrate whether the anions actively participate in the reaction mechanism or not. We show this approach for gold(i) mediated addition of methanol to an alkyne. The reaction mechanism can proceed via monoaurated intermediates (e.g., in catalysis with [(IPr)AuX]) or via diaurated intermediates (e.g., in catalysis with [(PPh3)AuX]). We show that anions X- slightly affect the reaction rates, however the effect stays almost the same even after their encapsulation in the cavity of bambusurils. We also demonstrate that X- affects the overall reaction rate in the very same way as the reaction rate of the protodeauration step. All results are consistent with the indirect effect of X- by the acidity of the conjugated acid HX on the rate-determining step. There is no evidence that a direct involvement of X- would affect the reaction rate.

• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH

The ruthenium complexes [Ru(CYM)(p-Cl-dkt)(Cl)] (1), [Ru(CYM)(pta)(p-Cl-dkt)]PF6 (2), and [Ru(CYM)(pta)Cl2] (3, RAPTA-C) (CYM = para-cymene, p-Cl-dkt = 1-(4-chlorophenyl)-4,4,4-trifluorobutane-1,3-dione, pta = 1,3,5-triaza-7-phosphaadamantane) are biologically active and show anti-cancer activities, albeit with different mechanisms. To further understand these mechanisms, we compared their speciation in aqueous solutions with an amino acid (cysteine), with an amino acid derivative (N-acetylcysteine) and with a tripeptide (glutathione) by Mass Spectrometry (MS). Here, we show that all ruthenium complexes have high selectivity for cysteine and cysteine-derived molecules. On one hand, [Ru(CYM)(p-Cl-dkt)(Cl)] undergoes solvolysis in water and forms [Ru2(CYM)2(OH)3]+. Subsequently, all hydroxyl anions are exchanged by deprotonated cysteine. Infrared Photodissociation Spectroscopy (IRPD) showed that cysteine binds to the ruthenium atoms via the deprotonated thiol group and that sulfur bridges the ruthenium centers. On the other hand, the pta-bearing complexes remain monometallic and undergo only slow Cl or p-Cl-dkt exchange by deprotonated cysteine. Therefore, the pta ligand protects the ruthenium complexes from ligand exchange with water and from the formation of biruthenium clusters, possibly explaining why the mechanism of pta-bearing ruthenium complexes is not based on ROS production but on their reactivity as monometallic complexes.

• Publication type
• Journal Article MeSH