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Sengupta, P. R.; Sinha, Ramanath; De, G S

doi:10.1023/a:1012089608629

Cited by 21 publications

(9 citation statements)

References 15 publications

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“…A similar observation has also been reported with cysteine and Penicillamine in their coordination with cadmium(II) [11,12]. In the interaction of DL-Penicillamine with [Pt(en)(H 2 O) 2 ] 2+ at pH 4.0 the ligand is reported to have reacted as a (N, S) bidentate chelate [13]. This type of ligating mode is also assumed under our reaction conditions ( Figure 4).…”

Section: Effect Of Variation Of [Dl-pen] On the Reaction Ratesupporting

confidence: 88%

Kinetic and mechanistic studies on the interaction ofDL -Penicillamine with the hydroxopentaaquarhodium(III) ion

Mukhopadhyay¹,

Das

Ghosh

2005

Transition Met Chem

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The kinetics of interaction between DL-Penicillamine and [Rh(H 2 O) 5 OH] 2+ have been studied spectrophotometrically as a function of [Rh(H 2 O) 5 OH 2+ ], [DL-Pen], pH and temperature. The reaction has been monitored at 242 nm, the k max of the substituted complex and where the spectral difference between the reactant and product is a maximum. The reaction rate increases with [DL-Pen] and reaches a limiting value at a higher ligand concentration. From the experimental findings an associative interchange mechanism for the substitution process is suggested. The activation parameters (DH z ¼ 35.8 ± 1.6 kJ mol )1 , DS z ¼ )209 ± 5 J K )1 mol )1 ) support the proposition. The negative DG 0 ()13.6 kJ mol )1 ) for the first equilibrium step also supports the spontaneous formation of an outersphere association complex.

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Section: Effect Of Variation Of [Dl-pen] On the Reaction Ratesupporting

confidence: 88%

Kinetic and mechanistic studies on the interaction ofDL -Penicillamine with the hydroxopentaaquarhodium(III) ion

Mukhopadhyay¹,

Das

Ghosh

2005

Transition Met Chem

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“…The band at 3299-2928 cm −1 is assigned to overlapping of ν (asym) and ν (sym) motion of the -NH 2 group coordinated to platinum(II) in the product complex. The band at 538 cm −1 is also assigned as ν(Pt N) bond formation [32][33][34]. The band at 1600 cm −1 in the spectrum of adenosine mainly due to skeletal vibration, gained intensity and shifted to 1638 cm −1 .…”

Section: Job's Measurementsmentioning

confidence: 99%

Kinetics and mechanism of the interaction of adenosine withcis‐diaqua(cis‐1,2‐diaminocyclohexane)platinum(II) perchlorate in aqueous medium

Karmakar

Mallick

Mondal

et al. 2011

Int J of Chemical Kinetics

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The kinetics of the interaction of adenosine with cis- [Pt(cis-dach) (OH 2 ) 2 ] 2+ (dach = diaminocyclohexane) was studied spectrophotometrically as a function of [cis-[Pt(cisdach)(OH 2 ) 2 ] 2+ ], [adenosine], and temperature at a particular pH (4.0), where the substrate complex exists predominantly as the diaqua species and the ligand adenosine exists as a neutral molecule. The substitution reaction shows two consecutive steps: the first is the ligand-assisted anation followed by a chelation step. The activation parameters for both the steps have been evaluated using Eyring equation. The low negative value of H = 1 (43.1 ± 1.3 kJ mol −1 ) and the large negative value of S = 1 (−177 ± 4 J K −1 mol −1 ) along with H = 2 (47.9 ± 1.8 kJ mol −1 ) and S = 2 (−181 ± 6 J K −1 mol −1 ) indicate an associative mode of activation for both the aqua ligand substitution processes. The kinetic study was substantiated by infrared and electrospray ionization mass spectroscopic analysis. C 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 219

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“…N-heterocycles are less p-acceptors and better p-donors than six membered N-heterocycles [30]. The presence of electron withdrawing substituents on the arylazo group and imidazole group influences the p-acidity of the ligand.…”

Section: Interpretation Of Rate Datamentioning

confidence: 99%

“…The plots of Hammett-r values (for substituent R in Pd(RaaiEt/RaaiBz)Cl 2 complexes) versus log k are linear ( Figure 8). The slope of the Hammett correlation diagram is positive and is indicative of the transition state [26,30] for the rate-limiting step of the overall reaction. This fact supports nucleophilic association.…”

Section: Interpretation Of Rate Datamentioning

confidence: 99%

Interaction Between Pd(RaaiR′)Cl2 and Adenine: Reaction Dynamics and Mechanism [RaaiR′ = 1-alkyl-2-(arylazo)imidazole]

Saha

Ghosh

Mahapatra

2005

Transition Met Chem

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Nucleophilic substitution of Pd(RaaiR¢)Cl 2 [RaaiR¢=1-alkyl-2-(arylazo)imidazole, p-RAC 6 H 4 AN@NAC 3 H 2 NN-1-R¢; where R= H(a)/Me(b)/Cl(c) and R¢ = Et(1)/Bz(2)] with adenine (A) in MeCN-water (1:1) at 298 K, to form [Pd(A) 2 ]Cl 2 , has been studied spectrophotometrically under pseudo-first-order conditions and the analyses support a nucleophilic association path. The reaction follows the rate law, rate = {a+k [A] 2 0 g[Pd(RaaiR¢)Cl 2 ]: first-order in Pd(RaaiR¢)Cl 2 and second-order in A. The rate increases as follows: Pd(RaaiEt)Cl 2 (1) < Pd(RaaiBz)Cl 2 (2) and Pd(MeaaiR¢)Cl 2 (b) < Pd(HaaiR¢)Cl 2 (a) < Pd(ClaaiR¢)Cl 2 (c). External addition of Cl ) (LiCl) suppresses the rate (rate µ 1/[Cl ) ]). The activation parameters, D z H 0 and D z S 0 of the reactions were calculated from the Eyring plot and support the proposed mechanism.

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Cited by 21 publications

References 15 publications

Kinetic and mechanistic studies on the interaction ofDL -Penicillamine with the hydroxopentaaquarhodium(III) ion

Kinetic and mechanistic studies on the interaction ofDL -Penicillamine with the hydroxopentaaquarhodium(III) ion

Kinetics and mechanism of the interaction of adenosine withcis‐diaqua(cis‐1,2‐diaminocyclohexane)platinum(II) perchlorate in aqueous medium

Interaction Between Pd(RaaiR′)Cl2 and Adenine: Reaction Dynamics and Mechanism [RaaiR′ = 1-alkyl-2-(arylazo)imidazole]

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