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

Ken Sakai, Taro Tsubomura, Kazuko Matsumoto

Research output: Contribution to journalArticle

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Abstract

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.

Original languageEnglish
Pages (from-to)11-16
Number of pages6
JournalInorganica Chimica Acta
Volume213
Issue number1-2
DOIs
Publication statusPublished - Nov 1993
Externally publishedYes

Fingerprint

Platinum
Dimers
cleavage
platinum
dimers
sulfuric acid
Sulfuric acid
Ligands
Pyrrolidinones
Oxidation
nuclear magnetic resonance
ligands
oxidation
Nuclear magnetic resonance spectroscopy
Substitution reactions
Nuclear magnetic resonance
Oxidation-Reduction
substitutes
spectroscopy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Redox disproportionation cleavage of an α-pyrrolidonate-bridged mixed-valent tetranuclear platinum complex. / Sakai, Ken; Tsubomura, Taro; Matsumoto, Kazuko.

In: Inorganica Chimica Acta, Vol. 213, No. 1-2, 11.1993, p. 11-16.

Research output: Contribution to journalArticle

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abstract = "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.",
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T1 - Redox disproportionation cleavage of an α-pyrrolidonate-bridged mixed-valent tetranuclear platinum complex

AU - Sakai, Ken

AU - Tsubomura, Taro

AU - Matsumoto, Kazuko

PY - 1993/11

Y1 - 1993/11

N2 - 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.

AB - 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.

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