Platinum complexes acid hydrolysis

The complexes can be obtained from the reaction of a Rh1 complex with 02 (equation 5),37 from the reaction of a Com-superoxo complex with a reduced metal (equation 6),38 from the acid hydrolysis of a platinum-peroxo complex3 (equation 7) or from the reaction of potassium superoxide with rhodium (equation 8)40 or palladium complexes.41... 

From this evidence, Langford argued that the X group is essentially completely dissociated and acts as a solvated anion in the transition state of acid hydrolysis and that water is at most weakly bound in the transition state. Another example from reactions of square-planar platinum complexes is given in Section 12-6-2. 

Recent immunochemical studies have shown that antibodies against the c is-Pt(NH3)2-DNA complex formed in vitro do not recognize the platinum-DNA complex isolated from rats which have been treated with C s-DDP (64). The present results show that the platinum-DNA adducts isolated from treated bacteria and mammalian cells do not give the same electrophoresis patterns after acid hydrolysis as the corresponding adducts formed in vitro It seems that, in vivo some of the modes of fixation of platinum compounds to DNA may be different than those found in vitro. 

Chromium, Manganese, Cobalt, Nickel, Ruthenium, Rhodium, Platinum, and Uranium Complexes Metalloporphsrrin Complexes Metal Ions and Nucleic Acid Hydrolysis... 

Considerable advances in the detection of intracellular metabolites have been made and a detailed description is available for complexes containing 1,2-diaminocyclohexane as carrier ligand [124, 125]. In these studies the widespread interaction with amino acids has been demonstrated and the hydrolysis of [Pt(malonato) (dach)] occurs without the requirement of enzymatic activation, as originally hypothesized. Biotransformation of platinum complexes has also been demonstrated by NMR studies [126]. These studies are an important complement to those of the DNA interactions discussed in Chapter 4, in terms of the overall objective of describing the intracellular chemistry of platinum complexes as fully as possible. 

Cisplatin cannot be administered orally because stomach acid would cause its hydrolysis. It bonds to plasma protein. The kidneys eliminate about 30-70% of the original complex. The rest is transported by the blood stream through cell membranes of different organs and tumor cells. The complex hydrolysis is rather fast because of the low chloride concentration in the intracellular region. Therefore, the platinum complex in the cell is partly in aqua form (about 40% as [c(5-Pt"(NH3)2Cl(H20)] ). The aqua complex is kinetically labile since the coordinated water is weakly bonded, compared to Cl . In addition, when the Cl leaves the complex, its increased positive charge is likely to promote... 

The direction of nucleophilic attack was proved to be trans (from anti side of metal) using platinum complex bearing a prochiral olefin. The diastereomerically pure alkene-complex 5 reacted with an amine 6, to generate, after acid hydrolysis, (5)-amine salt 7 corresponding to frans-addition (Eq. 3) [33-35]. 

Complex Fluorides of Platinum iv).— Although hexafluoroplatinic(iv) acid cannot be synthesized in water, its hydrolysis is so slow that the alkali, alkaline-earth, and rare-earth salts have aU been made from the acid in aqueous solution. The crystal structure of the potassium salt shows that the hexafluoroplatinate(iv) ion possesses the regular octahedral shape expected for a dizg electron configuration. 

CE separations of inorganic anions are almost always carried out at an alkaline pH to ensure that the analytes will be in the ionic rather than the molecular form. However, a flow modifier must generally be used to reverse the direction of EOF. Thornton and Fritz found that excellent separations of anions are possible at pH values as low as 2.0 (HCl) or 1.8 with perchloric acid [5]. Special attention was paid to the anionic chloro complexes of gold (III) and the platinum group elements, which are more resistant to hydrolysis in more acidic solutions. By working at lower pH values, the capillary silanol groups are largely un-ionized and consequently the EOF is minimal. 

It has been shown that formation of diphenylphosphinous and diphenylphosphinito complexes of platinum by hydrolysis involves diphenylphosphinous acid as a... 

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