Kinetics and mechanism of formation of the platinum-thallium bond: The (CN)(5)Pt-Tl(CN)(3) (3-) complex
2003 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 42, no 21, 6907-6914 p.Article in journal (Refereed) Published
Formation kinetics of the metal-metal bonded [(CN)(5)PtTl(CN)(3)](3-) complex from Pt(CN)(4)(2-) and Tl(CN)(4)(-) has been studied in the pH range-of 5-10, using standard mix-and-measure spectrophotometric technique at pH 5-8 and stopped-flow method at pH > 8. The overall order of the reaction, Pt(CN)(4)(2-) + Tl(CN)(4)(-) reversible arrow [(CN)(5)PtTl(CN)(3)](3-), is 2 in the slightly acidic region and 3 in the alkaline region, which means first order for the two reactants in both cases and also for CN- at high pH. The two-term rate law corresponds to two different pathways via the Tl(CN)(3) and Tl(CN)(4)(-) complexes in acidic and alkaline solution, respectively. The two complexes are in fast equilibrium, and their actual concentration ratio is controlled by the concentration of free cyanide ion. The following expression was derived for the pseudo-first-order rate constant of the overall reaction: k(obs) = (k(1)(a)[Tl(CN)(4)(-)] + (k(1)(a)/K-f))(1/(1 + K-p[H+]))[CN-](free) + k(1)(b) [Tl(CN)(4)(-)] + (k(1)(b)/K-f), where k(1)(a) and k(1)(b) are the forward rate constants for the alkaline and slightly acidic paths, K-f is the stability constant of [(CN)(5)PtTI(CN)(3)](3-), and K-p is the protonation constant of cyanide ion. k(1)(a) = 143 +/- 13 M-2 s(-1), k(1)(b) = 0.056 +/- 0.004 M-1 s(-1), K-f = 250 +/- 54 M-1, and log K-p = 9.15 +/- 0.05 (l = 1 M NaClO4, T = 298 K). Two possible mechanisms were postulated for the overall reaction in both pH regions, which include a metal-metal bond formation step and the coordination of the axial cyanide ion to the platinum center. The alternative mechanisms are different in the sequence of these steps.
Place, publisher, year, edition, pages
2003. Vol. 42, no 21, 6907-6914 p.
metal-metal bond, aqueous-solution, c-13 nmr, oxidative addition, cyanide complexes, hydrogen-cyanide, dissociation, spectroscopy, equilibrium, tl2pt(cn)4
IdentifiersURN: urn:nbn:se:kth:diva-22896DOI: 10.1021/ic034676hISI: 000186023900039OAI: oai:DiVA.org:kth-22896DiVA: diva2:341594
QC 201005252010-08-102010-08-10Bibliographically approved