Understanding the ring-opening, chelation and non-chelation reactions between nedaplatin and thiosulfate: a DFT study based on NBO, ETS-NOCV and QTAIM

Banerjee, Snehasis

doi:10.1007/s00214-015-1772-x

Cited by 7 publications

(6 citation statements)

References 60 publications

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“…Although, Alberto et al have investigated the hydrolysis mechanism of nedaplatin using DFT, they do not explicitly discuss structural and vibrational properties of nedaplatin. Banerjee also used DFT to analyze reactions of nedaplatin with thiosulfate rescue agents. Our computed bond lengths are in good agreement with those reported by Banerjee.…”

Section: Resultsmentioning

confidence: 99%

Raman and Infrared Studies of Platinum-Based Drugs: Cisplatin, Carboplatin, Oxaliplatin, Nedaplatin, and Heptaplatin

et al. 2018

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This study reports the optimized structures and lowest-energy conformations/stereochemistry of five currently used platinum-based drugs: cisplatin, carboplatin, nedaplatin, oxaliplatin, and heptaplatin. Normal Raman and IR spectra of each drug are experimentally obtained and have been compared to various levels of density functional theory (DFT). Although some combination of structure, reactivity, or spectroscopy for these drugs has been studied by various groups, there are no known experimental normal Raman and IR spectra for nedaplatin, oxaliplatin, and heptaplatin in the literature. The detailed structural and vibration findings of these drugs are very important to understanding platinum behavior and drug dynamics. The following work explores the vibrational frequencies of these drugs particularly by focusing on the low-energy modes between 200 and 600 cm, where anharmonicity effects will have less influence on the accuracy of computed frequencies. Ideally, the Pt-N stretching modes provide vibrational diagnostics for each drug. Interestingly, a vibrational energy decomposition analysis (VEDA) suggests that oxaliplatin and heptaplatin Pt-N stretching modes are not Raman or IR active. Instead, C-C and Pt-O stretching frequencies in the various bidentate dioxo ligands might be more useful in characterizing new cisplatin derivatives. Analysis of anharmonicity effects was compared against (and in tandem with) dimer computations of four of the five drugs. Harmonic vibrational computations of the dimeric cisplatin derivatives provided greater qualitative improvement than that of the monomeric derivatives. Satisfying agreement with experimental Raman spectra was obtained, even without resorting to linear scale factors for the harmonic dimer frequencies.

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Section: Resultsmentioning

confidence: 99%

Raman and Infrared Studies of Platinum-Based Drugs: Cisplatin, Carboplatin, Oxaliplatin, Nedaplatin, and Heptaplatin

et al. 2018

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“…Furthermore, when NOCV is associated with an energy decomposition analysis scheme [in particular with the extended transition state (ETS) method, initially developed by Ziegler and Rauk], it is possible to give a quantitative (i.e., energetic) description of the σ‐donor ( E σ ) and π‐acceptor ( E π ) contributions to the metal–ligand bond. Thus, in the last years, the ETS‐NOCV approach has emerged as a very precious tool for shedding light on the nature of metal‐to‐ligand interactions, as documented in the different cases studied . In the present study, we applied ETS‐NOCV to a series of [Mo(CO) 4 (phen*)] complexes (phen* = substituted 1,10‐phenanthroline) with the purpose of describing and quantifying the σ‐donor and π‐acceptor properties of phen* depending on their substitution.…”

Section: Introductionmentioning

confidence: 99%

A Quantitative Description of the σ‐Donor and π‐Acceptor Properties of Substituted Phenanthrolines

et al. 2016

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The bond between molybdenum and substituted 1,10-phenanthroline ligands in a series of [Mo(CO)4(phen*)]\ud complexes has been studied by combining experimental data (νCO) with DFT calculations. First, natural orbitals for chemical valence (NOCV) were calculated: The resulting charge-transfer magnitudes (Δqi) associated with the deformation density channels (Δρi) were related to σ-donation and π-back-donation.\ud Then, energy decomposition analysis was performed by applying the extended transition state (ETS) scheme. The outcomes of the ETS-NOCV approach has allowed us to quantify the energetic contribution of both ligand-to-metal (Eσ) and metal-to ligand (Eπ) interactions. A new parameter (Tphen) has been introduced comprising both Eσ and Eπ and thus providing a descriptor for the overall electronic contribution given by phenanthrolines\ud to the metal–ligand bond. This was corroborated by the linear correlation found between Tphen and the νCO vibration\ud modes of [Mo(CO)4(phen*)] complexes, at least for those containing a 2,9-unsubstituted phenanthroline. The case of\ud [Mo(CO)4(phen*)] derivatives with a 2,9-substituted phen* is also discussed

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“…Efforts from the groups of Alejandro Toro-Labbe and Artur Michalak have focused on decomposition of the reaction force using the extended transition state (ETS) variational EDA technique [54][55][56] combined with analysis of the electron density changes based on natural orbitals for chemical valence (NOCV), 57,58 in the ETS-NOCV approach. [59][60][61][62] Their work highlights the utility of characterizing the driving and retarding intermolecular forces throughout a chemical reaction in the cases of the water assisted HCN/CNH isomerization, 63 metal assisted intramolecular proton transfer in thymine, 64 and double proton transfer in formamide-derived complexes. 65 To our knowledge, there have been no studies exploring the use of a perturbative approach for the decomposition of the reaction force.…”

Section: Introductionmentioning

confidence: 99%

Symmetry-Adapted Perturbation Theory Decomposition of the Reaction Force: Insights into Substituent Effects Involved in Hemiacetal Formation Mechanisms

Derricotte

2019

Preprint

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<div>The decomposition of the reaction force based on symmetry-adapted perturbation theory (SAPT) has been proposed. This approach was used to investigate the subtituent effects along the reaction coordinate pathway for the hemiacetal formation mechanism between methanol and substituted aldehydes of the form CX<sub>3</sub>CHO (X = H, F, Cl, and Br), providing a quantitative evaluation of the reaction-driving and reaction-retarding force components. Our results highlight the importance of more favorable electrostatic and induction effects in the reactions involving halogenated aldehydes that leads to lower activation energy barriers. These substituent effects are further elucidated by applying the functional-group partition of symmetry-adapted</div><div>perturbation theory (F-SAPT). The results show that the reaction is largely driven by favorable direct non-covalent interactions between the CX<sub>3</sub> group on the aldehyde and the OH group on methanol.</div>

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Understanding the ring-opening, chelation and non-chelation reactions between nedaplatin and thiosulfate: a DFT study based on NBO, ETS-NOCV and QTAIM

Cited by 7 publications

References 60 publications

Raman and Infrared Studies of Platinum-Based Drugs: Cisplatin, Carboplatin, Oxaliplatin, Nedaplatin, and Heptaplatin

Raman and Infrared Studies of Platinum-Based Drugs: Cisplatin, Carboplatin, Oxaliplatin, Nedaplatin, and Heptaplatin

A Quantitative Description of the σ‐Donor and π‐Acceptor Properties of Substituted Phenanthrolines

Symmetry-Adapted Perturbation Theory Decomposition of the Reaction Force: Insights into Substituent Effects Involved in Hemiacetal Formation Mechanisms

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