A theoretical investigation on hydrolysis mechanism of biologically relevant Pt(II)/Pd(II) complexes with σ-donor and π-acceptor carrier ligand

• Published in: Chemical physics letters Vol. 657; pp. 148 - 155
• Main Authors: Reddy B., Venkata P., Mitra, Ishani, Mukherjee, Subhajit, Sengupta, P.S., Dodda, Subba Reddy, Moi, Sankar Ch
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 16.07.2016
• Subjects: 2-Aminomethylpyridine; DFT; Hydrolysis mechanism; Potential energy surface; Pt(II)/Pd(II) complexes; Potential energy surface; Hydrolysis mechanism; Pt(II)/Pd(II) complexes; DFT; 2-Aminomethylpyridine
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2016.06.004

[Display omitted] •Hydrolysis reaction mechanism of cisplatin analogous complexes have been studied.•Activation energies for two step hydrolysis calculated for both the complexes.•A concerted SN2 mechanism is proposed based on the structure of transition states.•First step of hydrolysis is faster than the second step for both the complexes 1 and 2. The hydrolysis mechanism of cytotoxic agents complex 1 cis-[Pt(pic)Cl2] and complex 2 cis-[Pd(pic)Cl2] (where pic=2-aminomethylpyridine) have been studied in solvent phase using DFT. The stationary states on potential energy surfaces were fully optimized and characterized. The rate constants and activation parameters of both the substitution processes has been calculated in CPCM model and the values were found to be k1=3.29×10−4s−1, k2=8.88×10−9s−1 for complex 1 and k1=0.13×10−1s−1, k2=2.0×10−10s−1 for complex 2 respectively. The second step is the rate-limiting process having higher activation energy compared to that of the first step for both the complexes.