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Aquation
About: Aquation is a research topic. Over the lifetime, 1443 publications have been published within this topic receiving 17507 citations.
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TL;DR: It is indicated that the fast hydrolysis of complex 2 may be attributed to the strong σ-donor ability of N-isopropyl-1R,2R-diaminocyclohexane, and an increasing ρ-donors ability of the amine group can promote the hydrolytic rate of the corresponding platinum(IV) complex.
Abstract: Platinum(IV) complexes are generally thought to be kinetically inert, and are expected to be stable enough to resist premature aquation before entering the cancer cells. Nevertheless, in this work, complex 2 with axial acetato ligands can hydrolyze relatively quickly under biologically relevant conditions with a half-life of 91.7 min, resulting in the loss of the equatorial chlorido ligand. Further study indicated that the fast hydrolysis of complex 2 may be attributed to the strong σ-donor ability of N-isopropyl-1R,2R-diaminocyclohexane, and an increasing σ-donor ability of the amine group can promote the hydrolysis rate of the corresponding platinum(IV) complex. The experiment results were proven by the corresponding DFT calculation. Our study can help to re-evaluate the aqueous properties of the platinum(IV) complexes with axial acetate, which may be less inert to hydrolysis than expected under biologically relevant conditions.
19 citations
TL;DR: In this article, the rate constants for the pathway kcat equal 2.5, 2.2, 32, 220 and 260 M 1 s 1 s 2 for complexes 2a,c, 4a ‐c and 4b,c, respectively, demonstrating that the benzylamine (4a) and a-methyl-benzylamines (4b) complexes are approximately ten and hundred times more active than N,N-dimethylbenzyamine complex 2a.
19 citations
TL;DR: In this paper, trifluoromethanesulphonato-O-O complexes were characterized spectroscopically, showing that co-coordinated CF3SO3H in these complexes may be substituted even by neutral co-ordinating O-donor solvents.
Abstract: Reaction of chloroplatinum(II) and chloropalladium(II) complexes containing amine, pyridine (py), or phosphine ligands at or above room temperature with anhydrous CF3SO3H leads to formation of trifluoromethanesulphonato-O complexes, characterized spectroscopically. The complexes cis-[Pt(NH3)2(OSO2CF3)2], trans-[Pt(NH3)2Cl(OSO2CF3)], [Pt(en)Cl(OSO2CF3)], (en = 1,2-diaminoethane), [Pt(dppe)(OSO2CF3)2], [Pt(py)2Cl(OSO2CF3)], [Pt(terpy)(OSO2CF3)][CF3SO3], (terpy = 2,2′: 6′,2″-terpyridine), trans-[Pd(NH3)2Cl(OSO2CF3)], [Pd(en)(OSO2CF3)2], [Pd(bippy)(OSO2CF3)2](bipy = 2,2′-bipyridine), and [Pd(PPh3)2(OSO2CF3)2] were isolated. Aquation reactions of selected complexes showed that trifluoromethanesulphonate hydrolysis is rapid for complexes of both PtII and PdII. Bis(trifluoromethanesulphonato)platinum(II) complexes exhibit two consecutive rate processes, with k1/k2ca. 5, consistent with sequential hydrolysis of both anions. Preliminary investigations indicate that co-ordinated CF3SO3– in these complexes may be substituted even by neutral co-ordinating O-donor solvents.
19 citations
TL;DR: In this paper, rate constants and activation parameters for the aquation of 12 saturated amines from pentacyanoamineferrate(I1) in 1 M pyridine solutions are reported.
Abstract: Rate constants and activation parameters for the aquation of 12 saturated amines from pentacyanoamineferrate(I1) in 1 M pyridine solutions are reported. While AG* values do not correlate with AGIO (for the ionization of the conjugate acid) or with u* and E, Taft's constants, an isokinetic relationship is found. For the series (CH3)xSH3_, and RSH2, AP correlates with A",' in water and each series shows an independent correlation of AS* with B,". These results are interpreted in terms of an adapted Caldin and Benetto's model for exchange reactions, the main contribution to the changes in activation parameters arising seemingly from the energetics of transfer of the released ligand to bulk water. This small contribution to the activation process in water is rendered observable by the remarkable insensitivity of the rate process to "inner" bonding effects.
19 citations