Kinetics and mechanism of platinum-thallium bond formation: The binuclear [(CN)5Pt-TI(CN)]- and the trinuclear [(CN) 5Pt-TI-Pt(CN)5]3- complex

Péter Nagy, Imre Tóth, I. Fábián, Mikhail Maliarik, Julius Glaser

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Abstract

Formation kinetics of the metal-metal bonded binuclear [(CN) 5Pt-TI(CN)- (1) and the trinuclear [(CN) 5Pt-TI-Pt-(CN)5]3- (2) complexes is studied, using the standard mix-and-measure spectrophotometric method. The overall reactions are Pt(CN)4 2- + TI(CN)2 + ⇌ 1 and Pt(CN)4 2- + [(CN)5Pt-TI(CN)] - ⇌ 2. The corresponding expressions for the pseudo-first-order rate constants are kobs = (k1[TI(CN) 2 +] + k-1)[TI(CN)2 +] (at TI(CN)2 + excess) and kobs = (k 2b[Pt(CN)4 2-] + k-2b)[HCN] (at Pt(CN)4 2- excess), and the computed parameters are k 1 = 1.04 ± 0.02 M-2 s-1, k-1 = k1/K1, = 7 x 10-5 M-1 s -1 and k2b = 0.45 ± 0.04 M-2 s -1, K2b = 26 ± 6 M-1, k-2b = k2b/K2b = 0.017 M-1 s-1, respectively. Detailed kinetic models are proposed to rationalize the rate laws. Two important steps need to occur during the complex formation in both cases: (i) metal-metal bond formation and (ii) the coordination of the fifth cyanide to the platinum site in a nucleophilic addition. The main difference in the formation kinetics of the complexes is the nature of the cyanide donor in step ii. In the formation of [(CN)5Pt-TI(CN)]-, TI(CN) 2 + is the source of the cyanide ligand, while HCN is the cyanide donating agent in the formation of the trinuclear species. The combination of the results with previous data predict the following reactivity order for the nucleophilic agents: CN- > TI(CN)2 + > HCN.

Original languageEnglish
Pages (from-to)5216-5221
Number of pages6
JournalInorganic Chemistry
Volume43
Issue number17
DOIs
Publication statusPublished - Aug 23 2004

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Thallium
thallium
Cyanides
Platinum
platinum
Metals
cyanides
Kinetics
kinetics
metals
Rate constants
Ligands
reactivity
ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

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Kinetics and mechanism of platinum-thallium bond formation : The binuclear [(CN)5Pt-TI(CN)]- and the trinuclear [(CN) 5Pt-TI-Pt(CN)5]3- complex. / Nagy, Péter; Tóth, Imre; Fábián, I.; Maliarik, Mikhail; Glaser, Julius.

In: Inorganic Chemistry, Vol. 43, No. 17, 23.08.2004, p. 5216-5221.

Research output: Contribution to journalArticle

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title = "Kinetics and mechanism of platinum-thallium bond formation: The binuclear [(CN)5Pt-TI(CN)]- and the trinuclear [(CN) 5Pt-TI-Pt(CN)5]3- complex",
abstract = "Formation kinetics of the metal-metal bonded binuclear [(CN) 5Pt-TI(CN)- (1) and the trinuclear [(CN) 5Pt-TI-Pt-(CN)5]3- (2) complexes is studied, using the standard mix-and-measure spectrophotometric method. The overall reactions are Pt(CN)4 2- + TI(CN)2 + ⇌ 1 and Pt(CN)4 2- + [(CN)5Pt-TI(CN)] - ⇌ 2. The corresponding expressions for the pseudo-first-order rate constants are kobs = (k1[TI(CN) 2 +] + k-1)[TI(CN)2 +] (at TI(CN)2 + excess) and kobs = (k 2b[Pt(CN)4 2-] + k-2b)[HCN] (at Pt(CN)4 2- excess), and the computed parameters are k 1 = 1.04 ± 0.02 M-2 s-1, k-1 = k1/K1, = 7 x 10-5 M-1 s -1 and k2b = 0.45 ± 0.04 M-2 s -1, K2b = 26 ± 6 M-1, k-2b = k2b/K2b = 0.017 M-1 s-1, respectively. Detailed kinetic models are proposed to rationalize the rate laws. Two important steps need to occur during the complex formation in both cases: (i) metal-metal bond formation and (ii) the coordination of the fifth cyanide to the platinum site in a nucleophilic addition. The main difference in the formation kinetics of the complexes is the nature of the cyanide donor in step ii. In the formation of [(CN)5Pt-TI(CN)]-, TI(CN) 2 + is the source of the cyanide ligand, while HCN is the cyanide donating agent in the formation of the trinuclear species. The combination of the results with previous data predict the following reactivity order for the nucleophilic agents: CN- > TI(CN)2 + > HCN.",
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T1 - Kinetics and mechanism of platinum-thallium bond formation

T2 - The binuclear [(CN)5Pt-TI(CN)]- and the trinuclear [(CN) 5Pt-TI-Pt(CN)5]3- complex

AU - Nagy, Péter

AU - Tóth, Imre

AU - Fábián, I.

AU - Maliarik, Mikhail

AU - Glaser, Julius

PY - 2004/8/23

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N2 - Formation kinetics of the metal-metal bonded binuclear [(CN) 5Pt-TI(CN)- (1) and the trinuclear [(CN) 5Pt-TI-Pt-(CN)5]3- (2) complexes is studied, using the standard mix-and-measure spectrophotometric method. The overall reactions are Pt(CN)4 2- + TI(CN)2 + ⇌ 1 and Pt(CN)4 2- + [(CN)5Pt-TI(CN)] - ⇌ 2. The corresponding expressions for the pseudo-first-order rate constants are kobs = (k1[TI(CN) 2 +] + k-1)[TI(CN)2 +] (at TI(CN)2 + excess) and kobs = (k 2b[Pt(CN)4 2-] + k-2b)[HCN] (at Pt(CN)4 2- excess), and the computed parameters are k 1 = 1.04 ± 0.02 M-2 s-1, k-1 = k1/K1, = 7 x 10-5 M-1 s -1 and k2b = 0.45 ± 0.04 M-2 s -1, K2b = 26 ± 6 M-1, k-2b = k2b/K2b = 0.017 M-1 s-1, respectively. Detailed kinetic models are proposed to rationalize the rate laws. Two important steps need to occur during the complex formation in both cases: (i) metal-metal bond formation and (ii) the coordination of the fifth cyanide to the platinum site in a nucleophilic addition. The main difference in the formation kinetics of the complexes is the nature of the cyanide donor in step ii. In the formation of [(CN)5Pt-TI(CN)]-, TI(CN) 2 + is the source of the cyanide ligand, while HCN is the cyanide donating agent in the formation of the trinuclear species. The combination of the results with previous data predict the following reactivity order for the nucleophilic agents: CN- > TI(CN)2 + > HCN.

AB - Formation kinetics of the metal-metal bonded binuclear [(CN) 5Pt-TI(CN)- (1) and the trinuclear [(CN) 5Pt-TI-Pt-(CN)5]3- (2) complexes is studied, using the standard mix-and-measure spectrophotometric method. The overall reactions are Pt(CN)4 2- + TI(CN)2 + ⇌ 1 and Pt(CN)4 2- + [(CN)5Pt-TI(CN)] - ⇌ 2. The corresponding expressions for the pseudo-first-order rate constants are kobs = (k1[TI(CN) 2 +] + k-1)[TI(CN)2 +] (at TI(CN)2 + excess) and kobs = (k 2b[Pt(CN)4 2-] + k-2b)[HCN] (at Pt(CN)4 2- excess), and the computed parameters are k 1 = 1.04 ± 0.02 M-2 s-1, k-1 = k1/K1, = 7 x 10-5 M-1 s -1 and k2b = 0.45 ± 0.04 M-2 s -1, K2b = 26 ± 6 M-1, k-2b = k2b/K2b = 0.017 M-1 s-1, respectively. Detailed kinetic models are proposed to rationalize the rate laws. Two important steps need to occur during the complex formation in both cases: (i) metal-metal bond formation and (ii) the coordination of the fifth cyanide to the platinum site in a nucleophilic addition. The main difference in the formation kinetics of the complexes is the nature of the cyanide donor in step ii. In the formation of [(CN)5Pt-TI(CN)]-, TI(CN) 2 + is the source of the cyanide ligand, while HCN is the cyanide donating agent in the formation of the trinuclear species. The combination of the results with previous data predict the following reactivity order for the nucleophilic agents: CN- > TI(CN)2 + > HCN.

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