A kinetic investigation of mononuclear trans-platinum(II) complexes with mixed amine ligands

Olusegun, Moses Ariyo; Reddy, D. Mohan; Jaganyi, Deogratius

doi:10.1007/s11243-020-00381-0

Cited by 3 publications

(5 citation statements)

References 33 publications

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“…Computational modeling using the density functional theoretical (DFT) calculations was akin to those described in Olusegun et al, 22,24 and the results obtained are in good agreement with those obtained in our previous studies. A closer look at Table 1 reveals a corresponding decrease in the natural bond orbital (NBO) charges on the platinum(II) ions as the amine moieties become bulkier in all the trans-platinum(II) complexes with symmetric amine ligands (tPt, tPtM, and tPtR).…”

Section: Methodssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

“…The synthesized complexes and the preparation of aqua complexes were achieved following the procedure described in the literature 22,24 . The chemical characterization: 1 H‐NMR spectral, mass spectral, and UV‐vis spectral data were in excellent agreement with those obtained in earlier preparations.…”

Section: Methodsmentioning

confidence: 99%

“…The study advanced that the reaction kinetics of the complexes are comparable to that of cisplatin. Olusegun et al 24 have also reported the substitution behavior of some mononuclear trans ‐platinum(II) complexes with mixed or asymmetrical amine ligands. In an effort to gain an in‐depth understanding of the substitution behavior of these mononuclear trans ‐platinum(II) complexes, it is imperative to explore a comparative study of the substitution behavior of some bifunctional mononuclear trans ‐platinum(II) complexes with symmetrical and asymmetrical alkylamine ligands.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Methodssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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“…[18] Note that the elongation of the chain length of the alkylamine group in the cis position with respect to the leaving ligand had a negligible effect on the electronic structure of the complex but decreased the rate of substitution reactions due to increased steric hindrance. [43]…”

Section: Hydrocarbon Substituentsmentioning

confidence: 99%

Tuning the Reactivity and Bonding Properties of the Pt(II) Complexes by the Substitution(s) on the Trans‐Coordinated Non‐Aromatic Amine Ligand

Dvořáčková

Chval

2021

ChemistrySelect

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Kinetics of the hydration reaction and the bonding properties of the trans-[Pt(NH 3 ) 2 (NH 2 X)Cl] + complexes (X = H, CH 3 , F, Cl, Br, NH 2 , NO 2 , OH, dimethylamine (DMA), cyclopropyl (CyP), cyclohexyl (CyH)) were studied theoretically by DFT methodology in the gas phase and the water solution. The electrondonating and electron-withdrawing X substituents lower and increase, respectively, the activation free energy (ΔG � ) and Pttrans ligand binding energies (BEs) to a similar extent as meta and para substituents of the pyridine ligand studied previously (ACS Omega, 2020, 5, 11768). For the saturated hydrocarbon X substituents (X = H, CH 3 , CyP, CyH), the ΔG � values and Pt-trans ligand BEs decrease with the logarithm of the X substituent size being best quantified by the number of electrons. The additivity of the substituent effects was studied on the NF 3 ligand and worked well for ligand charges and PtÀ trans ligand BEs. The influence of chelation was evaluated by the comparison of the CyH system and the complexes with the cyclohexanediamine (DACH) ligand. Finally, the effect of isomerization was studied on the complexes with the 1,2-bis (aminomethyl)cyclobutane (BAMCB) ligand. Thus, this study also evaluates the influence of the non-leaving ligands present in cisplatin, oxaliplatin, lobaplatin, JM118, and JM11 drugs on the reactivity of the Pt(II) complexes in the same ligand environment.

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Understanding the role of flexible alkyl-α,ω-diamine linkers on the substitution behaviour of dinuclear trans-platinum(II) complexes: A kinetic and mechanistic study

Olusegun

Reddy

Jaganyi

2021

Inorganica Chimica Acta

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A kinetic investigation of mononuclear trans-platinum(II) complexes with mixed amine ligands

Cited by 3 publications

References 33 publications

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

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

Tuning the Reactivity and Bonding Properties of the Pt(II) Complexes by the Substitution(s) on the Trans‐Coordinated Non‐Aromatic Amine Ligand

Understanding the role of flexible alkyl-α,ω-diamine linkers on the substitution behaviour of dinuclear trans-platinum(II) complexes: A kinetic and mechanistic study

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