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

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

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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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