Thermodynamic and kinetic stabilization of divanadate in the monovanadate/divanadate equilibrium using a Zn-cyclene derivative: Towards a simple ATP synthase model

• Hanno Sell,
• Anika Gehl,
• Frank D. Sönnichsen and
• Rainer Herges

Beilstein J. Org. Chem. 2012, 8, 81–89, doi:10.3762/bjoc.8.8

• thermodynamically as shown by NMR titration. Moreover, EXSY NMR experiments reveal that the vanadate dimer is also kinetically stabilized with respect to hydrolysis by complexation with Zn-cyclene. Keywords: EXSY NMR; NMR titration; supramolecular chemistry; vanadate condensation; 51V NMR; Zn-cyclene

• Zn-cyclene units in an appropriate distance to allow multiple coordination to the phosphate oxygen atoms [15]. Brown et al. were able to catalyze the cyclization (hydrolysis/intramolecular condensation) of 2-hydroxypropyl aryl phosphate using a tethered dimeric Zn-triazacyclododecane [16]. Lehn et al

• condensation reactions, we focused on the influence of benzyl Zn-tetraazacyclododecane (Zn-benzylcyclene) 1 on the aggregation of vanadate in water. According to DFT calculations (B3LYP/6-31G*) of a number of different geometries, the monovanadate anion is bound to the Zn-cyclene unit by forming one