The effect of alkyl chain tethers on the kinetics and mechanistic behaviour of bifunctional dinuclear platinum(<scp>ii</scp>) complexes bearing <i>N</i>,<i>N</i>′-dipyridylamine ligands

Wangoli, Panyako Asman; Kinunda, Grace

doi:10.1039/c7nj03021e

Cited by 7 publications

(2 citation statements)

References 87 publications

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“…Figure 4 shows the Eyring plots for all the three nucleophiles, and the results are summarized in Table 3 (also see Tables S2‐S11 in the Supporting Information). A moderately positive activation enthalpy in all the investigated complexes and a negative activation entropy favor an association mechanism, which is ubiquitous in most d 8 square planar complexes 50‐54 …”

Section: Resultsmentioning

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: Resultsmentioning

confidence: 99%

“…A moderately positive activation enthalpy in all the investigated complexes and a negative activation entropy favor an association mechanism, which is ubiquitous in most d 8 square planar complexes. [50][51][52][53][54]…”

Section: Complexmentioning

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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Proximity effects on the phosphorescent properties of dinuclear salicylaldiminato cyclometalated iridium(III) complexes linked with polymethylene spacers

Kawamorita

Ahadito

2019

Transit Met Chem

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The influence of α,α′-diimine bridging ligand on the reactivity of binuclear para-cymene ruthenium(II) complexes. Kinetic, mechanistic and computational study

Mutua

Onunga

Sitati

et al. 2021

Inorganica Chimica Acta

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The effect of alkyl chain tethers on the kinetics and mechanistic behaviour of bifunctional dinuclear platinum(ii) complexes bearing N,N′-dipyridylamine ligands

Abstract: This study reports on non-classical dinuclear platinum(ii) complexes, with the ability to bind to DNA strands in a different manner from cisplatin and its analogues. This is an effort to design dinuclear Pt(ii) complexes that target DNA and are bifunctional.

Cited by 7 publications

References 87 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

Proximity effects on the phosphorescent properties of dinuclear salicylaldiminato cyclometalated iridium(III) complexes linked with polymethylene spacers

The influence of α,α′-diimine bridging ligand on the reactivity of binuclear para-cymene ruthenium(II) complexes. Kinetic, mechanistic and computational study

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