Preparation and structural characterization of mono-Ru-substituted α2-Dawson-type phosphotungstate with a carbonyl ligand and other Ru(CO)-substituted heteropolytungstates

Kensuke Nishiki, Hiromi Ota, Shuhei Ogo, Tsuneji Sano, Masahiro Sadakane

Research output: Contribution to journalArticle

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Abstract

In our previous article (Dalton Trans. 2008, 6692-6698) we reported that hydrothermal reaction of a mono-lacunary Keggin-type silicotungstate, [SiW11O39]8-, and Ru(acac)3 (acac: acetylacetonate) for 5-24 h produced a mono-Ru-substituted Keggin-type silicotungstate with a terminal aqua ligand, [SiW11O39RuIII(H2O)]5-, which was further converted into a carbonyl (CO) derivative, [SiW11O39RuII(CO)]6-, by increasing the reaction time for several days. Here, reactions of Ru(acac)3 with other mono-lacunary heteropolytungstates for the formation of other mono-Ru(CO)-substituted heteropolytungstates, including Keggin derivatives, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, and Dawson-type phosphotungstates, [α1-P2W17O61RuII(CO)]8- and [α2-P2W17O61RuII(CO)]8-, are presented. The desired α2-isomer of Dawson-type phosphotungstate, [α2-P2W17O61RuII(CO)]8-, was produced in high purity and was fully characterized by CV, 31P NMR, 13C NMR, IR, UV/Vis, elemental analysis, mass spectroscopy, TG-DTA, TPD-MS, and single-crystal structure analysis. On the other hand, Keggin-type complexes, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, were formed together with their aqua derivatives, [GeW11O39RuIII(H2O)]5- and [PW11O39RuIII(H2O)]4-, respectively, and the α1-isomer of Dawson-type phosphotungstate, [α1-P2W17O61RuII(CO)]8-, was produced together with the α2-derivative, as confirmed by CV, IR, mass spectroscopy, and 31P NMR spectroscopy.

Original languageEnglish
Pages (from-to)2714-2723
Number of pages10
JournalEuropean Journal of Inorganic Chemistry
Volume2015
Issue number16
DOIs
Publication statusPublished - 2015 Jun 1
Externally publishedYes

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Ligands
Derivatives
Isomers
Nuclear magnetic resonance
Spectroscopy
Temperature programmed desorption
Differential thermal analysis
Nuclear magnetic resonance spectroscopy
Crystal structure
Single crystals
Chemical analysis
acetyl acetonate

Keywords

  • Carbonyl ligands
  • Polyoxometalates
  • Ruthenium
  • Structure elucidation
  • Tungsten

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Preparation and structural characterization of mono-Ru-substituted α2-Dawson-type phosphotungstate with a carbonyl ligand and other Ru(CO)-substituted heteropolytungstates. / Nishiki, Kensuke; Ota, Hiromi; Ogo, Shuhei; Sano, Tsuneji; Sadakane, Masahiro.

In: European Journal of Inorganic Chemistry, Vol. 2015, No. 16, 01.06.2015, p. 2714-2723.

Research output: Contribution to journalArticle

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abstract = "In our previous article (Dalton Trans. 2008, 6692-6698) we reported that hydrothermal reaction of a mono-lacunary Keggin-type silicotungstate, [SiW11O39]8-, and Ru(acac)3 (acac: acetylacetonate) for 5-24 h produced a mono-Ru-substituted Keggin-type silicotungstate with a terminal aqua ligand, [SiW11O39RuIII(H2O)]5-, which was further converted into a carbonyl (CO) derivative, [SiW11O39RuII(CO)]6-, by increasing the reaction time for several days. Here, reactions of Ru(acac)3 with other mono-lacunary heteropolytungstates for the formation of other mono-Ru(CO)-substituted heteropolytungstates, including Keggin derivatives, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, and Dawson-type phosphotungstates, [α1-P2W17O61RuII(CO)]8- and [α2-P2W17O61RuII(CO)]8-, are presented. The desired α2-isomer of Dawson-type phosphotungstate, [α2-P2W17O61RuII(CO)]8-, was produced in high purity and was fully characterized by CV, 31P NMR, 13C NMR, IR, UV/Vis, elemental analysis, mass spectroscopy, TG-DTA, TPD-MS, and single-crystal structure analysis. On the other hand, Keggin-type complexes, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, were formed together with their aqua derivatives, [GeW11O39RuIII(H2O)]5- and [PW11O39RuIII(H2O)]4-, respectively, and the α1-isomer of Dawson-type phosphotungstate, [α1-P2W17O61RuII(CO)]8-, was produced together with the α2-derivative, as confirmed by CV, IR, mass spectroscopy, and 31P NMR spectroscopy.",
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T1 - Preparation and structural characterization of mono-Ru-substituted α2-Dawson-type phosphotungstate with a carbonyl ligand and other Ru(CO)-substituted heteropolytungstates

AU - Nishiki, Kensuke

AU - Ota, Hiromi

AU - Ogo, Shuhei

AU - Sano, Tsuneji

AU - Sadakane, Masahiro

PY - 2015/6/1

Y1 - 2015/6/1

N2 - In our previous article (Dalton Trans. 2008, 6692-6698) we reported that hydrothermal reaction of a mono-lacunary Keggin-type silicotungstate, [SiW11O39]8-, and Ru(acac)3 (acac: acetylacetonate) for 5-24 h produced a mono-Ru-substituted Keggin-type silicotungstate with a terminal aqua ligand, [SiW11O39RuIII(H2O)]5-, which was further converted into a carbonyl (CO) derivative, [SiW11O39RuII(CO)]6-, by increasing the reaction time for several days. Here, reactions of Ru(acac)3 with other mono-lacunary heteropolytungstates for the formation of other mono-Ru(CO)-substituted heteropolytungstates, including Keggin derivatives, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, and Dawson-type phosphotungstates, [α1-P2W17O61RuII(CO)]8- and [α2-P2W17O61RuII(CO)]8-, are presented. The desired α2-isomer of Dawson-type phosphotungstate, [α2-P2W17O61RuII(CO)]8-, was produced in high purity and was fully characterized by CV, 31P NMR, 13C NMR, IR, UV/Vis, elemental analysis, mass spectroscopy, TG-DTA, TPD-MS, and single-crystal structure analysis. On the other hand, Keggin-type complexes, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, were formed together with their aqua derivatives, [GeW11O39RuIII(H2O)]5- and [PW11O39RuIII(H2O)]4-, respectively, and the α1-isomer of Dawson-type phosphotungstate, [α1-P2W17O61RuII(CO)]8-, was produced together with the α2-derivative, as confirmed by CV, IR, mass spectroscopy, and 31P NMR spectroscopy.

AB - In our previous article (Dalton Trans. 2008, 6692-6698) we reported that hydrothermal reaction of a mono-lacunary Keggin-type silicotungstate, [SiW11O39]8-, and Ru(acac)3 (acac: acetylacetonate) for 5-24 h produced a mono-Ru-substituted Keggin-type silicotungstate with a terminal aqua ligand, [SiW11O39RuIII(H2O)]5-, which was further converted into a carbonyl (CO) derivative, [SiW11O39RuII(CO)]6-, by increasing the reaction time for several days. Here, reactions of Ru(acac)3 with other mono-lacunary heteropolytungstates for the formation of other mono-Ru(CO)-substituted heteropolytungstates, including Keggin derivatives, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, and Dawson-type phosphotungstates, [α1-P2W17O61RuII(CO)]8- and [α2-P2W17O61RuII(CO)]8-, are presented. The desired α2-isomer of Dawson-type phosphotungstate, [α2-P2W17O61RuII(CO)]8-, was produced in high purity and was fully characterized by CV, 31P NMR, 13C NMR, IR, UV/Vis, elemental analysis, mass spectroscopy, TG-DTA, TPD-MS, and single-crystal structure analysis. On the other hand, Keggin-type complexes, [GeW11O39RuII(CO)]6- and [PW11O39RuII(CO)]5-, were formed together with their aqua derivatives, [GeW11O39RuIII(H2O)]5- and [PW11O39RuIII(H2O)]4-, respectively, and the α1-isomer of Dawson-type phosphotungstate, [α1-P2W17O61RuII(CO)]8-, was produced together with the α2-derivative, as confirmed by CV, IR, mass spectroscopy, and 31P NMR spectroscopy.

KW - Carbonyl ligands

KW - Polyoxometalates

KW - Ruthenium

KW - Structure elucidation

KW - Tungsten

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EP - 2723

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JF - European Journal of Inorganic Chemistry

SN - 1434-1948

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