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Kinetic and mechanistic studies of the interaction of 2-mercapto pyridine with dichloro[1-alkyl-2-(arylazo)imidazole]palladium(II) complexes

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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 2-Mercaptopyridine (2-SH-Py) in acetonitrile (MeCN) at 298 K, to form [Pd2(2-S-Py)4], has been studied spectrophotometrically under pseudo-first-order conditions and the analyses support the nucleophilic association path. The reaction follows the rate law, Rate  =  {k 0  +   k [2-SH-Py] 20 }[Pd(RaaiR′)Cl2]: first order in Pd(RaaiR′)Cl2 and second order in 2-SH-Py. The rate of the reaction follows the order: 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) and HCl suppresses the rate (Rate ∝ 1/[Cl−]0 & ∝1/[HCl]0). The reactions have been studied at different temperatures (293–308 K) and activation parameters (Δ‡ H° and Δ ‡ S°) of the reactions were calculated from the Eyring plot and support the proposed mechanism.

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

    Sushanta Saha, Tapas Majumdar & Ambikesh Mahapatra

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  1. Sushanta Saha
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  2. Tapas Majumdar
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  3. Ambikesh Mahapatra
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Correspondence to Ambikesh Mahapatra.

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Saha, S., Majumdar, T. & Mahapatra, A. Kinetic and mechanistic studies of the interaction of 2-mercapto pyridine with dichloro[1-alkyl-2-(arylazo)imidazole]palladium(II) complexes. Transition Met Chem 31, 1017–1023 (2006). https://doi.org/10.1007/s11243-006-0101-6

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