Kinetic and mechanistic studies of 1,3-bis(2-pyridylimino)isoindolate Pt(<scp>ii</scp>) derivatives. Experimental and new computational approach

Wekesa, Isaac Masika; Jaganyi, Deogratius

doi:10.1039/c3dt52272e

Cited by 29 publications

(10 citation statements)

References 88 publications

(128 reference statements)

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“…Pt(II) complexes with ve-membered N^N^N tridentate ligand chelates react much faster than sixmembered N^N^N tridentate ligand chelates. 10,18,20 This can also be explained by the argument already presented.…”

Section: +supporting

confidence: 55%

Seven membered chelate Pt(ii) complexes with 2,3-di(2-pyridyl)quinoxaline ligands: studies of substitution kinetics by sulfur donor nucleophiles, interactions with CT-DNA, BSA and in vitro cytotoxicity activities

et al. 2019

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Section: +supporting

confidence: 55%

Seven membered chelate Pt(ii) complexes with 2,3-di(2-pyridyl)quinoxaline ligands: studies of substitution kinetics by sulfur donor nucleophiles, interactions with CT-DNA, BSA and in vitro cytotoxicity activities

et al. 2019

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“…The absolute value of HOMO gives the ionisation potential (I), whereas LUMOs correspond to electron affinity (A). [48] Again, chemical hardness (η) can be evaluated by Equation 4.…”

Section: Dft Studymentioning

confidence: 99%

Anticancer activity and biomolecular interaction of Pt(II) complexes: Their synthesis, characterisation and DFT study

Mandal

Reddy

Mitra

et al. 2021

Applied Organom Chemis

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Cis-[Pt (TEEDA)Cl 2 ]; 1 (where TEEDA = N,N,N 0 -triethylethylenediamine) was synthesised, and its SCXRD structure was determined. Complex 1 crystallises in the monoclinic space group I2/a; (z = 8) and unit cell parameters are a = 15.1919(4) Å; b = 9.6049(3) Å; c = 16.7825 Å; α = 90.00 ; β = 94.784(3) and γ = 90.00 . Complex 1 was hydrolysed to diaqua species cis-[Pt (TEEDA)(H 2 O) 2 ] 2+ ; 2 L-cysteine (L-cys) and N-acetyl-L-cysteine (N-ac-L-cys) chelated complex cis-[Pt (TEEDA)(L-cys)] + 3 and cis-[Pt (TEEDA)(N-ac-L-cys)] 4 were synthesised and characterised by spectroscopic methods. Kinetic study of substitution reactions of Complex 2 to Complexes 3 and 4 have been explored with the thiols L-cys and N-ac-L-cys, respectively. The theoretical study with density functional theory (DFT) has been considered to optimise the structures of Complexes 1-4 for HOMO-LUMO energy calculation, TD-DFT simulation and natural bond orbital (NBO) analysis to support structural characterisation of the complexes. Various electronic properties, known as DFT-based descriptors, have been calculated from frontier molecular orbital energies to correlate with the adduct formation aptitude of the complexes with DNA and BSA. The binding aptitude and binding mode of the complexes with DNA and BSA have been performed by UV-Vis and spectrofluorometric titration methods. To observe the interaction of the complexes with CT-DNA, gel electrophoresis experiment has been carried out. A molecular docking study of the complexes was performed with DNA and BSA. The anticancer activity and ROS generation of the complexes were investigated on different cancer cell lines and fibroblast cells with DCF-DA using FITC filter. K E Y W O R D S anticancer activity, DNA and BSA binding, kinetics and mechanism, MTT assay and DFT study, Pt(II) complex Saikat Mandal and Venkata P. Reddy B. contributed equally to this research work.

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“…However, the electrophilicity index (ω) of both complexes agrees with their respective p K a value. Essentially, the electrophilicity index is superior to the NBO charge in predicting electrophilicity and reactivity of a complex because the NBO charge indicates only the individual atomic charge, whereas the electrophilicity index describes the resulting charge of the entire complex 34,46 . In general, p K a values are usually associated with the electrophilicity of the metal center 47 .…”

Section: Resultsmentioning

confidence: 99%

“…Essentially, the electrophilicity index is superior to the NBO charge in predicting electrophilicity and reactivity of a complex because the NBO charge indicates only the individual atomic charge, whereas the electrophilicity index describes the resulting charge of the entire complex. 34,46 In general, pK a values are usually associated with the electrophilicity of the metal center. 47 Moreover, on the basis of the DFT descriptors, such as NBO charges, electronic chemical potential, chemical hardness, and electrophilicity index, one would expect the transplatinum(II) complexes with asymmetric amines, tPt2H 2 O and tPt3H 2 O, to exhibit the same pK a values.…”

Section: Pk a Determination Of The Diaqua Complexesmentioning

confidence: 99%

An investigation of comparative substitution behavior of bifunctional trans‐platinum(II) complexes with symmetric and asymmetric alkylamine ligands

Olusegun

Reddy

Jaganyi

2020

Int J of Chemical Kinetics

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This study was undertaken to investigate the comparative substitution behavior of mononuclear trans-platinum(II) complexes with symmetric and asymmetric amine ligands. The rate of substitution of the aqua moeities from the complexes trans-[Pt(NH 3) 2 (H 2 O) 2 ](ClO 4) 2 (tPt), trans-[Pt(NH 3)(NH 2 C 2 H 5)(H 2 O) 2 ] (ClO 4) 2 (tPt2H 2 O), trans-[Pt(NH 3)(NH 2 C 3 H 7)(H 2 O) 2 ](ClO 4) 2 (tPt3H 2 O), [trans-Pt(OH 2) 2 (NH 2 CH 3) 2 ](ClO 4) 2 (tPtM), and [trans-Pt(OH 2) 2 {NH 2 CH(CH 3) 2 } 2 ] (ClO 4) 2 (tPtR), by three nucleophiles, namely thiourea (TU), 1,3-dimethylthiourea (DMTU), and 1,1,3,3-tetramethylthiourea (TMTU) was studied under pseudo-first-order conditions as a function of concentration and temperature by stopped-flow spectrophotometry. All the substitution reactions of each of the trans-platinum(II) complexes proceeds by a stepwise mechanism involving rate-determining substitution of the first aqua ligand followed by a fast second substitution step, without any intermediates formed. The reactions were second order overall (rate = k obs [complex] where k obs = k 2 [nucleophile]), first order in both [complex] and [nucleophile]. The reactivity of the complexes was essentially governed by both steric and electronic factors. Comparing the second-order rate constants for the substitution reactions of the mononuclear diaqua trans-platinum(II) complexes with the thiourea-based nucleophiles, the observed trend follows: tPt > tPt2H 2 O > tPtM > tPt3H 2 O > tPtR. This reactivity trend is consistent with the pK a values obtained for the first deprotonation step. The reactivity of the nucleophiles with the complexes decreases with an increase in steric demand in the following order: TU > DMTU > TMTU. The low positive values of activation enthalpy and large negative values of activation entropy indicate an associative mechanism of substitution in all the complexes. The computational modeling using density functional theory calculations was employed to provide theoretical interpretation of kinetic data.

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Kinetic and mechanistic studies of 1,3-bis(2-pyridylimino)isoindolate Pt(ii) derivatives. Experimental and new computational approach

Cited by 29 publications

References 88 publications

Seven membered chelate Pt(ii) complexes with 2,3-di(2-pyridyl)quinoxaline ligands: studies of substitution kinetics by sulfur donor nucleophiles, interactions with CT-DNA, BSA and in vitro cytotoxicity activities

Seven membered chelate Pt(ii) complexes with 2,3-di(2-pyridyl)quinoxaline ligands: studies of substitution kinetics by sulfur donor nucleophiles, interactions with CT-DNA, BSA and in vitro cytotoxicity activities

Anticancer activity and biomolecular interaction of Pt(II) complexes: Their synthesis, characterisation and DFT study

An investigation of comparative substitution behavior of bifunctional trans‐platinum(II) complexes with symmetric and asymmetric alkylamine ligands

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