Kinetics and mechanism of reaction of α-picolinic acid with dichloro-{2-(arylazo)- heterocycle}palladium(II) complexes
-
G. K. Rauth
Abstract
The reaction between Pd(N,N')Cl2 [(N,N'= l-methyl-2-(arylazo)imidazole (RaaiMe), p-RC6H4- N=N-C3H2NN-1 -Me; 2-(arylazo)pyridine (Raap), p-C6H4-N=N-C5H4N; 2- (arylazo)pyrimidine (Raapm), p-C6H4-N=N-C4H3N2; where R=H (a), Me (b), CI (c)] and apicolinic acid (α-picH) have been examined spectrophotometrically in MeCN solution at 298K. The product is Pd(a-pic)2 which has been supported by pure compound synthesis from Na2[PdCl4] and α-picH. The kinetics of the nucleophilic substitution reaction has been studied under pseudo-first-order condition. The reaction proceeds in a biphasic manner. The kinetic analysis confirms the nucleophilic association path. External addition of CI- (LiCl) suppresses the rate. On considering the consecutive reaction A-> B-> C the rate data have been evaluated. Each phase shows first-order dependence on [α-picH]. Rate-1 = {a1+k1[(α-picH]}[ Pd(N,N')Cl2]; rate-2 = {a1+k2[(α-picH]}[Pd(N,N')Cl2], with the k1 (first phase rate constant) > k2 (second phase rate constant). Increase in π-acidity of the ligand N,N' increases the rate and follows the order: Pd(RaaiMe)Cl2 < Pd(Raap)Cl2 < Pd(Raapm)Cl2 .
© 2014 by Walter de Gruyter Berlin/Boston
Artikel in diesem Heft
- Kinetics and Mechanism of the Reaction of Ninhydrin with Chromium(III)-tryptophan Complex in Absence and Presence of Surfactants
- Site of Bond Breaking in mer-(Dihapto-[60]fullerene) (Dihapto-1,2-Bis-(DiphenyIphosphino)ethane Tricarbonyl Tungsten(0)
- Kinetic and mechanistic studies of mono(terpyridine)- to bis(terpyridine)-nickel(II) complex formation reactions involving a range of substituted 2,2′:6′,2″-terpyridine ligands: an investigation of π-stacking interactions in outer-sphere complexes.
- Kinetics and mechanism of reaction of α-picolinic acid with dichloro-{2-(arylazo)- heterocycle}palladium(II) complexes
- Simulation of Complex Chemical Kinetics
- Kinetics and Mechanisms of the Reduction of Chromium(VI) by 2-Mercaptoethanesulfonic Acid in Aqueous Solution: Difference in the Mechanistic Process of Reduction with Noncarboxylate Thiols
- Salt Effects on Reactivity for Substitution Reactions of Pentacyanoferrate(II) Complexes
- Substitution of aqua ligands from ds-[Pt(en)(H2O)2](ClO4)2 and cis-[Pt(dmen)(H2O)2](ClO4)2 (en = ethylenediamine, dmen = Ν,Ν′-dimethylethylenediamine) by glutathione (reduced) (GSH) in aqueous medium - A Kinetic And Mechanistic Study.
- Synthesis, Characterisation and Dissociation of a Glycinate Bridged Trinuclear Co(III)-Cu(II)-Co(III) Complex
- Notes for Contributors. Inorganic Reaction Mechanisms (IRM)
Artikel in diesem Heft
- Kinetics and Mechanism of the Reaction of Ninhydrin with Chromium(III)-tryptophan Complex in Absence and Presence of Surfactants
- Site of Bond Breaking in mer-(Dihapto-[60]fullerene) (Dihapto-1,2-Bis-(DiphenyIphosphino)ethane Tricarbonyl Tungsten(0)
- Kinetic and mechanistic studies of mono(terpyridine)- to bis(terpyridine)-nickel(II) complex formation reactions involving a range of substituted 2,2′:6′,2″-terpyridine ligands: an investigation of π-stacking interactions in outer-sphere complexes.
- Kinetics and mechanism of reaction of α-picolinic acid with dichloro-{2-(arylazo)- heterocycle}palladium(II) complexes
- Simulation of Complex Chemical Kinetics
- Kinetics and Mechanisms of the Reduction of Chromium(VI) by 2-Mercaptoethanesulfonic Acid in Aqueous Solution: Difference in the Mechanistic Process of Reduction with Noncarboxylate Thiols
- Salt Effects on Reactivity for Substitution Reactions of Pentacyanoferrate(II) Complexes
- Substitution of aqua ligands from ds-[Pt(en)(H2O)2](ClO4)2 and cis-[Pt(dmen)(H2O)2](ClO4)2 (en = ethylenediamine, dmen = Ν,Ν′-dimethylethylenediamine) by glutathione (reduced) (GSH) in aqueous medium - A Kinetic And Mechanistic Study.
- Synthesis, Characterisation and Dissociation of a Glycinate Bridged Trinuclear Co(III)-Cu(II)-Co(III) Complex
- Notes for Contributors. Inorganic Reaction Mechanisms (IRM)
