Solution equilibria leading to the formation of metal-metal bonds in partially oxidized bisoxalatoplatinate(II) systems

Barbara J. Keller; Stephanie K. Hurst; Steven O. Dunham; Lee Spangler; Edwin H. Abbott; Eric S. Peterson

doi:10.1016/j.ica.2003.09.009

Solution equilibria leading to the formation of metal-metal bonds in partially oxidized bisoxalatoplatinate(II) systems

Barbara J. Keller, Stephanie K. Hurst, Steven O. Dunham, Lee Spangler, Edwin H. Abbott, Eric S. Peterson

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

The reaction between [Pt^II(Ox)₂]^2- and an appropriate oxidant resulted in the formation of the dimeric unbridged platinum complex [{Pt^III(Ox)₂ }₂]^2- where (Ox) is oxalate. This complex was moderately stable under ambient conditions and was studied via a variety of NMR and spectrophotometric techniques. Reaction of the [{Pt^III(Ox)₂}₂]^2- complex with [Pt^II(Ox)₂]^2- in the presence of H⁺ lead to the formation of a series of longer platinum oligomers with non-integral oxidation states, culminating in the formation of partially oxidized platinum polymers of general formula [{Pt(Ox)₂} _n]^n-. The concentration of H⁺ was an important factor leading to higher oligomers and the approximate number of protons associated with each oligomer was determined. The analogous [{Pt ^III(Mal)₂}₂]^2- complex, where (Mal) is the malonate anion, was also synthesized and studied but was shown to be significantly less stable.

Original language	English (US)
Pages (from-to)	853-858
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	357
Issue number	3
DOIs	https://doi.org/10.1016/j.ica.2003.09.009
State	Published - Feb 20 2004

Keywords

Dimer
Oxalato
Partially oxidized
Platinum
Polymer

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2003.09.009

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title = "Solution equilibria leading to the formation of metal-metal bonds in partially oxidized bisoxalatoplatinate(II) systems",

abstract = "The reaction between [PtII(Ox)2]2- and an appropriate oxidant resulted in the formation of the dimeric unbridged platinum complex [{PtIII(Ox)2 }2]2- where (Ox) is oxalate. This complex was moderately stable under ambient conditions and was studied via a variety of NMR and spectrophotometric techniques. Reaction of the [{PtIII(Ox)2}2]2- complex with [PtII(Ox)2]2- in the presence of H+ lead to the formation of a series of longer platinum oligomers with non-integral oxidation states, culminating in the formation of partially oxidized platinum polymers of general formula [{Pt(Ox)2} n]n-. The concentration of H+ was an important factor leading to higher oligomers and the approximate number of protons associated with each oligomer was determined. The analogous [{Pt III(Mal)2}2]2- complex, where (Mal) is the malonate anion, was also synthesized and studied but was shown to be significantly less stable.",

keywords = "Dimer, Oxalato, Partially oxidized, Platinum, Polymer",

author = "Keller, {Barbara J.} and Hurst, {Stephanie K.} and Dunham, {Steven O.} and Lee Spangler and Abbott, {Edwin H.} and Peterson, {Eric S.}",

note = "Funding Information: The work described in this paper was supported by The Associated Western Universities, the Inland Northwest Research Alliance, and the United States Department of Energy through Contract # DE-AC07-99ID13727. The authors also wish to thank Johnson-Matthey Corporation for generous loans of platinum. ",

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T1 - Solution equilibria leading to the formation of metal-metal bonds in partially oxidized bisoxalatoplatinate(II) systems

AU - Keller, Barbara J.

AU - Hurst, Stephanie K.

AU - Dunham, Steven O.

AU - Spangler, Lee

AU - Abbott, Edwin H.

AU - Peterson, Eric S.

N1 - Funding Information: The work described in this paper was supported by The Associated Western Universities, the Inland Northwest Research Alliance, and the United States Department of Energy through Contract # DE-AC07-99ID13727. The authors also wish to thank Johnson-Matthey Corporation for generous loans of platinum.

PY - 2004/2/20

Y1 - 2004/2/20

N2 - The reaction between [PtII(Ox)2]2- and an appropriate oxidant resulted in the formation of the dimeric unbridged platinum complex [{PtIII(Ox)2 }2]2- where (Ox) is oxalate. This complex was moderately stable under ambient conditions and was studied via a variety of NMR and spectrophotometric techniques. Reaction of the [{PtIII(Ox)2}2]2- complex with [PtII(Ox)2]2- in the presence of H+ lead to the formation of a series of longer platinum oligomers with non-integral oxidation states, culminating in the formation of partially oxidized platinum polymers of general formula [{Pt(Ox)2} n]n-. The concentration of H+ was an important factor leading to higher oligomers and the approximate number of protons associated with each oligomer was determined. The analogous [{Pt III(Mal)2}2]2- complex, where (Mal) is the malonate anion, was also synthesized and studied but was shown to be significantly less stable.

AB - The reaction between [PtII(Ox)2]2- and an appropriate oxidant resulted in the formation of the dimeric unbridged platinum complex [{PtIII(Ox)2 }2]2- where (Ox) is oxalate. This complex was moderately stable under ambient conditions and was studied via a variety of NMR and spectrophotometric techniques. Reaction of the [{PtIII(Ox)2}2]2- complex with [PtII(Ox)2]2- in the presence of H+ lead to the formation of a series of longer platinum oligomers with non-integral oxidation states, culminating in the formation of partially oxidized platinum polymers of general formula [{Pt(Ox)2} n]n-. The concentration of H+ was an important factor leading to higher oligomers and the approximate number of protons associated with each oligomer was determined. The analogous [{Pt III(Mal)2}2]2- complex, where (Mal) is the malonate anion, was also synthesized and studied but was shown to be significantly less stable.

KW - Dimer

KW - Oxalato

KW - Partially oxidized

KW - Platinum

KW - Polymer

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Solution equilibria leading to the formation of metal-metal bonds in partially oxidized bisoxalatoplatinate(II) systems

Abstract

Keywords

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