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

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Abstract

Nucleophilic substitution of Pd(RaaiR′)Cl2 [RaaiR′=1-alkyl-2-(arylazo)imidazole, p-R—C6H4— N=N—C3H2NN-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]Cl2, 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] 02[Pd(RaaiR′)Cl2]: first-order in Pd(RaaiR′)Cl2 and second-order in A. The rate increases as follows: Pd(RaaiEt)Cl2(1) < Pd(RaaiBz)Cl2(2) and Pd(MeaaiR′)Cl2(b) < Pd(HaaiR′)Cl2(a) < Pd(ClaaiR′)Cl2(c). External addition of Cl− (LiCl) suppresses the rate (rate 1/[Cl−]). The activation parameters, \( \delta_\ddagger \)H0 and \( \delta_\ddagger \)S0 of the reactions were calculated from the Eyring plot and support the proposed mechanism.

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Authors and Affiliations

  1. Department of Chemistry, Jadavpur University, 700 032, Kolkata, India

    Sushanta Saha, Pradip Kumar Ghosh & Ambikesh Mahapatra

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  1. Sushanta Saha
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  2. Pradip Kumar Ghosh
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  3. Ambikesh Mahapatra
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Correspondence to Ambikesh Mahapatra.

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Saha, S., Ghosh, P.K. & Mahapatra, A. Interaction Between Pd(RaaiR′)Cl2 and Adenine: Reaction Dynamics and Mechanism [RaaiR′ = 1-alkyl-2-(arylazo)imidazole]. Transition Met Chem 30, 706–711 (2005). https://doi.org/10.1007/s11243-005-6243-0

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