Kinetic study of the ligand substitution on the trimethylplatinum(IV) complexes with unidentate ligands

Yuichi Kondo, Yumi Oda, Koji Ishihara

研究成果: Article

2 被引用数 (Scopus)

抄録

Ligand substitution kinetics for the reaction [PtIVMe3(X)(NN)] + NaY = [PtIVMe3(Y)(NN)] + NaX, where NN = bipy or phen, X = MeO-, CH3COO-, or HCOO-, and Y = SCN- or N3-, has been studied in methanol at various temperatures. The kinetic parameters for the reaction are as follows. The reaction of [PtMe3(OMe)(phen)] with NaSCN: k1 = 36.1 ± 10.0 s-1; ΔH1 = 65.9 ± 14.2 kj mol-1; ΔS1 = 6 ± 47 J mol-1 K-1; k2 = 0.0355 ± 0.0034 s-1; ΔH-2 = 63.8 ± 1.1 kJ mol-1; ΔS-2 = -58.8 ± 3.6 J mol-1 K-1; and k-1/k2 = 148 ± 19. The reaction of [PtMe3(OAc)(bipy)] with NaN3: k1 = 26.2 ± 0.1 s-1; ΔH1 = 60.5 ± 6.6 kJ mol-1; ΔS1 = -14 ± 22 J mol-1K-1; k-2 = 0.134 ± 0.081 s-1; ΔH-2 = 74.1 ± 24.3 kJ mol-1; ΔS-2 = -10 ± 82 J mol-1K-1; and k-1/k2 = 0.479 ± 0.012. The reaction of [PtMe3(OAc)(bipy)] with NaSCN; k1 = 26.4 ± 0.3 s-1; ΔH1 = 59.6 ± 6.7 kJ mol-1; ΔS1 = -17 ± 23 J mol-1K-1; k-2 = 0.174 ± 0.200 s-1; ΔH-2 = 62.7 ± 10.3 kJ mol-1; ΔS-2 = -48 ± 35 J mol-1K-1 and k-1/k2 = 1.01 ± 0.08. The reaction of [PtMe3(OOCH)(bipy)] with NaN3: k1 = 36.8 ± 0.3 s-1; ΔH1 = 66.4 ± 4.7 kJ mol-1; ΔS1 = 7 ± 16 J mol-1K-1; k-2 = 0.164 ± 0.076 s-1; ΔH-2 = 47.0 ± 18.1 kJ mol-1; ΔS-2 = -101 ± 61 J mol-1 K-1; and k-1/k2 = 5.90 ± 0.18. The reaction of [PtMe3(OOCH)(bipy)] with NaSCN: k1 = 33.5 ± 0.2 s-1; ΔH1 = 58.0 ± 0.4 kJ mol-1; ΔS1 = -20.5 ± 1.6 J mol-1 K-1; k-2 = 0.222 ± 0.083 s-1; ΔH-2 = 54.9 ± 6.3 kJ mol-1; ΔS-2 = -73.0 ± 21.3 J mol-1 K-1; and k-1/k2 = 12.0 ± 0.3. Conditional pseudo-first-order rate constant k0 increased linearly with the concentration of NaY, while it decreased drastically with the concentration of NaX. Some plausible mechanisms were examined, and the following mechanism was proposed.>

本文言語English
ページ(範囲)523-532
ページ数10
ジャーナルInternational Journal of Chemical Kinetics
30
8
DOI
出版ステータスPublished - 1998 1 1

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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