Cobalt(III) complex promoted hydrolysis of phosphate diesters: change in rate-determining step with change in phosphate diester reactivity

Incorporation of Cobalt‐Cyclen Complexes into Templated Nanogels Results in Enhanced Activity

“…There is no significant difference between the catalysed reactions and the background, suggesting that product inhibitiono ccurs,afinding consistentw ith previously reported data for these systems. [43] The next step focused on the evaluation of the catalytic activity of the cobalt-cyclen nanogels P1 and P2.A st he characterisation data clearly indicate (see Table S1 in the Supporting Information), the content of cobalt differs for the two preparations, therefore in ordert oe nsure accurate data, experiments were carried out using different amounts of polymers to ensure equal concentration of active sites. The reactions were carried out under identical experimental conditions, with 442 mm and 664 mm of substrate 1 and 100 mm [Co] for both P1 and P2,w hichr epresent 23 %a nd 15 %c atalytic load re- Figure 4.…”

Effects of N-alkyl and ammonium groups on the hydrolytic cleavage of DNA with a Cu(II)TACH (1,3,5-triaminocyclohexane) complex. Speciation, kinetic, and DNA-binding studies for reaction mechanism

“…One of coordinated water molecules is deprotonated in CuL 2+ , while both the ammonium group as well as one of coordinated water molecules is deprotonated in CuLH þ À1 . Because the pK a of an aliphatic ammonium group (9-11) is generally higher than the pK a of coordinated water (7)(8) of Cu(II)-1,3-propanediamine [56]. The monomeric dihydroxo structure was assigned to CuLH À2 on the basis of the high EPR intensity at pH 9.5.…”

“…As a result, it has been revealed that complexes of transition metals such as Fe(III), Co(II), Co(III), Cu(II), Zn(II) and the lanthanides La(III), Ce(IV) are capable of promoting hydrolysis of the phosphodiester bonds of activated substrates such as BNPP (bis(p-nitrophenyl)phosphate) [1][2][3][4][8][9][10][11][12]14,16,17,19,20,23,24,[27][28][29][30][31][32][33][34], BDNPP (bis(2,4-dinitrophenyl)phosphate) [1][2][3][4]8,9,18,25], ENP (ethyl pnitrophenyl phosphate) [1][2][3][4]11,13,14], EDNP (ethyl 2,4-dinitrophenyl phosphate) [1][2][3][4]22,24,26] and natural plasmid DNAs [1][2]...…”

Bis[μ-bis(4-nitrophenyl)phosphato-κ2O:O′]bis{[bis(2-pyridylmethyl)amine-κ3N,N′,N′′′]copper(II)} diperchlorate acetonitrile hemisolvate

“…Cu II complexes of chelating N-donor ligands are well known to catalyze the hydrolysis of phosphate esters. The phosphate diester bis(4-nitrophenyl)phosphate (bnpp) has been used in model studies of the kinetics of the catalysis of the hydrolysis phosphate esters by Cu II complexes (Deschamps et al, 2002;Fry et al, 2005;Linkletter & Chin, 1995;Stern et al, 1990), among other complexes of transition metals (Chin & Zou, 1988). In our experiments to study the catalytic properties of the complex [Cu(bpa)(H 2 O) 2 ](ClO 4 ) 2 (Gultneh et al, 1999) formed in solution, for the hydrolysis of the diester, bnpp, under conditions of a large excess of Na + (bnpp) À added in dimethylformamide (DMF), we isolated the title dinuclear Cu II compound, (I), containing a -1,3bridged activated phosphoester ligand (Jurek & Martell, 1999).…”