Kinetics and mechanism of reaction of α-picolinic acid with dichloro-{2-(arylazo)- heterocycle}palladium(II) complexes
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| 024 | 7 | 0 | |a 10.1515/irm-2003-0104 |2 doi |
| 035 | |a (NATIONALLICENCE)gruyter-10.1515/irm-2003-0104 | ||
| 245 | 0 | 0 | |a Kinetics and mechanism of reaction of α-picolinic acid with dichloro-{2-(arylazo)- heterocycle}palladium(II) complexes |h [Elektronische Daten] |c [G. K. Rauth, Sk. Jasimuddin, A. Mahapatra, C. Sinha] |
| 520 | 3 | |a 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 . | |
| 540 | |a © 2014 by Walter de Gruyter Berlin/Boston | ||
| 690 | 7 | |a Palladium(II) |2 nationallicence | |
| 690 | 7 | |a substitution reaction |2 nationallicence | |
| 690 | 7 | |a arylazoheterocycle |2 nationallicence | |
| 690 | 7 | |a α-picolinic acid |2 nationallicence | |
| 690 | 7 | |a biphasic |2 nationallicence | |
| 690 | 7 | |a π-acidity |2 nationallicence | |
| 700 | 1 | |a Rauth |D G. K. |4 aut | |
| 700 | 1 | |a Jasimuddin |D Sk |4 aut | |
| 700 | 1 | |a Mahapatra |D A. |4 aut | |
| 700 | 1 | |a Sinha |D C. |4 aut | |
| 773 | 0 | |t BioInorganic Reaction Mechanisms |d De Gruyter |g 5/1(2003-01-01), 31-38 |x 2191-2483 |q 5:1<31 |1 2003 |2 5 |o irm | |
| 856 | 4 | 0 | |u https://doi.org/10.1515/irm-2003-0104 |q text/html |z Onlinezugriff via DOI |
| 908 | |D 1 |a research article |2 jats | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1515/irm-2003-0104 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Rauth |D G. K. |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Jasimuddin |D Sk |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Mahapatra |D A. |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Sinha |D C. |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t BioInorganic Reaction Mechanisms |d De Gruyter |g 5/1(2003-01-01), 31-38 |x 2191-2483 |q 5:1<31 |1 2003 |2 5 |o irm | ||
| 900 | 7 | |b CC0 |u http://creativecommons.org/publicdomain/zero/1.0 |2 nationallicence | |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-gruyter | ||