Redox disproportionation cleavage of an α-pyrrolidonate-bridged mixed-valent tetranuclear platinum complex

Ken Sakai, Taro Tsubomura, Kazuko Matsumoto

研究成果: Contribution to journalArticle査読

14 被引用数 (Scopus)

抄録

The solution properties of α-pyrrolidonate-bridged dinuclear and tetranuclear platinum complexes are described. The general formula of the compounds is [Pt2(NH3)4(C4H6NO)2]nm+, where C4H6NO=deprotonated α-pyrrolidone, n=1 or 2, m=2-4 per dimer unit. The charge m depends on the average Pt oxidation state in the range 2.0-3.0 (the complex takes the four oxidation states PtII2, PtII3PtIII, PtII2PtIII2, and PtIII2). The behavior of the mixed- valent tetranuclear platinum complex[PtIIPtIII(NH3)4(C4H6NO)2]26+ (n=2,m=6) in aqueous media was investigated by means of UV-Vis and 1H NMR spectroscopy. It was shown that [PtIIPtIII(NH3)4(C4H6NO)2]26+ undergoes a rapid disproportionation cleavage into the dinuclear complexes [PtII2(NH3)4(C4H6NO)2]2+ (n=1, m=2) and [PtIII2(NH3)4(C4H6NO)2LL′]4+ (n=1, m=4; L, L′ are axial ligands). It was also found that the reaction is a reversible process and the equilibrium is largely shifted to the side of the dimers. A 1H NMR study on the solution of [PtIIPtIII(NH3)4(C4H6NO)2]26+ confirms the formation of the two dimers in the molar ratio of c. 1:1. An equilibrium study on the axial ligand substitution of [PtIII2(NH3)4(C4H6NO)2(H2O)2]4+ shows the existence of three different chemical species, diaqua-, aqua-sulfato- and disulfato-coordinated PtIII2 dimers, in aqueous sulfuric acid solution. The study also confirms that the disproportionation cleavage of [PtIIPtIII(NH3)4(C4H6NO)2]26+ in aqueous sulfuric acid solution produces these PtIII2 dimers.

本文言語英語
ページ(範囲)11-16
ページ数6
ジャーナルInorganica Chimica Acta
213
1-2
DOI
出版ステータス出版済み - 11 1993
外部発表はい

All Science Journal Classification (ASJC) codes

  • 物理化学および理論化学
  • 無機化学
  • 材料化学

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