Preparation and redox studies of α1- and α2-isomers of mono-Ru-substituted dawson-type phosphotungstates with a DMSO Ligand: [α12-P 2W17O61RuII(DMSO)]8-

Shuhei Ogo, Noriko Shimizu, Kensuke Nishiki, Nobuhiro Yasuda, Tsutomu Mizuta, Tsuneji Sano, Masahiro Sadakane

Research output: Contribution to journalArticle

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Abstract

Both α1- and α2-isomers of mono-Ru-substituted Dawson-type heteropolytungstates with a DMSO ligand, [α1-P2W17O61Ru II(DMSO)]8- and [α2-P2W 17O61RuII(DMSO)]8-, are prepared from the α2-isomer of a monolacunary derivative, [α2-P2W17O61]10-. Reaction of [α2-P2W17O61] 10- with Ru(DMSO)4Cl2 under hydrothermal conditions produces [α2-P2W17O 61RuII(DMSO)]8- as a main product together with [α1-P2W17O61Ru II(DMSO)]8-, [PW11O39Ru II(DMSO)]5-, and [P2W18O 62]6- as byproducts. By addition of KCl to the reaction mixture, K82-P2W17O 61RuII(DMSO)] is isolated in a moderate yield. On the other hand, reaction of [α2-P2W17O 61]10- with Ru2(benzene)2Cl 4 under hydrothermal conditions produces an isomeric mixture of [P2W17O61RuIII(H2O)] 7-1-isomer/α2-isomer ratio: ca. 8/1) as a main product together with [PW11O39Ru III(H2O)]4- and [P2W 18O62]6- as byproducts. By addition of acetone to the reaction mixture, K7[P2W17O 61RuIII(H2O)] is isolated in a good yield. Reaction of [P2W17O61RuIII(H 2O)]7- with DMSO produces [α1-P 2W17O61RuIII(DMSO)]7- as a main product and [α2-P2W17O 61RuIII(DMSO)]7- as a minor product. By addition of KCl and acetone, the α1-isomer K 81-P2W17O 61RuII(DMSO)] is isolated in a good yield. Both compounds are fully analyzed by CV, NMR (1H, 13C, 31P, and 183W), IR, UV-vis, elemental analysis, mass spectroscopy, and single-crystal structure analysis. Assuming that isomerization does not occur during the reaction of [P2W17O61Ru III(H2O)]7- with DMSO, the isolated [P 2W17O61RuIII(H2O)] 7- contains the α1-isomer as a main compound with the α2-isomer as a minor compound. Unusual transformation of the α2-isomer of [P2W17O 61]10- to the α1-isomer occurs. Redox behaviors of [α1-P2W17O 61RuII(DMSO)]8- and [α2-P 2W17O61RuII(DMSO)]8- are compared together with Ru(DMSO)-substituted α-Keggin-type heteropolytungstates, [α-XW11O39Ru(DMSO)] n- (X = Si, Ge, and P).

Original languageEnglish
Pages (from-to)3526-3539
Number of pages14
JournalInorganic Chemistry
Volume53
Issue number7
DOIs
Publication statusPublished - 2014 Apr 7
Externally publishedYes

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Dimethyl Sulfoxide
Isomers
isomers
Ligands
preparation
ligands
products
acetone
Oxidation-Reduction
Acetone
Byproducts
isomerization
mass spectroscopy
benzene
nuclear magnetic resonance
crystal structure
single crystals
Isomerization
Benzene

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Preparation and redox studies of α1- and α2-isomers of mono-Ru-substituted dawson-type phosphotungstates with a DMSO Ligand : [α12-P 2W17O61RuII(DMSO)]8-. / Ogo, Shuhei; Shimizu, Noriko; Nishiki, Kensuke; Yasuda, Nobuhiro; Mizuta, Tsutomu; Sano, Tsuneji; Sadakane, Masahiro.

In: Inorganic Chemistry, Vol. 53, No. 7, 07.04.2014, p. 3526-3539.

Research output: Contribution to journalArticle

Ogo, Shuhei ; Shimizu, Noriko ; Nishiki, Kensuke ; Yasuda, Nobuhiro ; Mizuta, Tsutomu ; Sano, Tsuneji ; Sadakane, Masahiro. / Preparation and redox studies of α1- and α2-isomers of mono-Ru-substituted dawson-type phosphotungstates with a DMSO Ligand : [α12-P 2W17O61RuII(DMSO)]8-. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 7. pp. 3526-3539.
@article{b3cb8440e78c4f63aba2ff1e6e9b8b1d,
title = "Preparation and redox studies of α1- and α2-isomers of mono-Ru-substituted dawson-type phosphotungstates with a DMSO Ligand: [α1/α2-P 2W17O61RuII(DMSO)]8-",
abstract = "Both α1- and α2-isomers of mono-Ru-substituted Dawson-type heteropolytungstates with a DMSO ligand, [α1-P2W17O61Ru II(DMSO)]8- and [α2-P2W 17O61RuII(DMSO)]8-, are prepared from the α2-isomer of a monolacunary derivative, [α2-P2W17O61]10-. Reaction of [α2-P2W17O61] 10- with Ru(DMSO)4Cl2 under hydrothermal conditions produces [α2-P2W17O 61RuII(DMSO)]8- as a main product together with [α1-P2W17O61Ru II(DMSO)]8-, [PW11O39Ru II(DMSO)]5-, and [P2W18O 62]6- as byproducts. By addition of KCl to the reaction mixture, K8[α2-P2W17O 61RuII(DMSO)] is isolated in a moderate yield. On the other hand, reaction of [α2-P2W17O 61]10- with Ru2(benzene)2Cl 4 under hydrothermal conditions produces an isomeric mixture of [P2W17O61RuIII(H2O)] 7- (α1-isomer/α2-isomer ratio: ca. 8/1) as a main product together with [PW11O39Ru III(H2O)]4- and [P2W 18O62]6- as byproducts. By addition of acetone to the reaction mixture, K7[P2W17O 61RuIII(H2O)] is isolated in a good yield. Reaction of [P2W17O61RuIII(H 2O)]7- with DMSO produces [α1-P 2W17O61RuIII(DMSO)]7- as a main product and [α2-P2W17O 61RuIII(DMSO)]7- as a minor product. By addition of KCl and acetone, the α1-isomer K 8[α1-P2W17O 61RuII(DMSO)] is isolated in a good yield. Both compounds are fully analyzed by CV, NMR (1H, 13C, 31P, and 183W), IR, UV-vis, elemental analysis, mass spectroscopy, and single-crystal structure analysis. Assuming that isomerization does not occur during the reaction of [P2W17O61Ru III(H2O)]7- with DMSO, the isolated [P 2W17O61RuIII(H2O)] 7- contains the α1-isomer as a main compound with the α2-isomer as a minor compound. Unusual transformation of the α2-isomer of [P2W17O 61]10- to the α1-isomer occurs. Redox behaviors of [α1-P2W17O 61RuII(DMSO)]8- and [α2-P 2W17O61RuII(DMSO)]8- are compared together with Ru(DMSO)-substituted α-Keggin-type heteropolytungstates, [α-XW11O39Ru(DMSO)] n- (X = Si, Ge, and P).",
author = "Shuhei Ogo and Noriko Shimizu and Kensuke Nishiki and Nobuhiro Yasuda and Tsutomu Mizuta and Tsuneji Sano and Masahiro Sadakane",
year = "2014",
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day = "7",
doi = "10.1021/ic403041s",
language = "English",
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pages = "3526--3539",
journal = "Inorganic Chemistry",
issn = "0020-1669",
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TY - JOUR

T1 - Preparation and redox studies of α1- and α2-isomers of mono-Ru-substituted dawson-type phosphotungstates with a DMSO Ligand

T2 - [α1/α2-P 2W17O61RuII(DMSO)]8-

AU - Ogo, Shuhei

AU - Shimizu, Noriko

AU - Nishiki, Kensuke

AU - Yasuda, Nobuhiro

AU - Mizuta, Tsutomu

AU - Sano, Tsuneji

AU - Sadakane, Masahiro

PY - 2014/4/7

Y1 - 2014/4/7

N2 - Both α1- and α2-isomers of mono-Ru-substituted Dawson-type heteropolytungstates with a DMSO ligand, [α1-P2W17O61Ru II(DMSO)]8- and [α2-P2W 17O61RuII(DMSO)]8-, are prepared from the α2-isomer of a monolacunary derivative, [α2-P2W17O61]10-. Reaction of [α2-P2W17O61] 10- with Ru(DMSO)4Cl2 under hydrothermal conditions produces [α2-P2W17O 61RuII(DMSO)]8- as a main product together with [α1-P2W17O61Ru II(DMSO)]8-, [PW11O39Ru II(DMSO)]5-, and [P2W18O 62]6- as byproducts. By addition of KCl to the reaction mixture, K8[α2-P2W17O 61RuII(DMSO)] is isolated in a moderate yield. On the other hand, reaction of [α2-P2W17O 61]10- with Ru2(benzene)2Cl 4 under hydrothermal conditions produces an isomeric mixture of [P2W17O61RuIII(H2O)] 7- (α1-isomer/α2-isomer ratio: ca. 8/1) as a main product together with [PW11O39Ru III(H2O)]4- and [P2W 18O62]6- as byproducts. By addition of acetone to the reaction mixture, K7[P2W17O 61RuIII(H2O)] is isolated in a good yield. Reaction of [P2W17O61RuIII(H 2O)]7- with DMSO produces [α1-P 2W17O61RuIII(DMSO)]7- as a main product and [α2-P2W17O 61RuIII(DMSO)]7- as a minor product. By addition of KCl and acetone, the α1-isomer K 8[α1-P2W17O 61RuII(DMSO)] is isolated in a good yield. Both compounds are fully analyzed by CV, NMR (1H, 13C, 31P, and 183W), IR, UV-vis, elemental analysis, mass spectroscopy, and single-crystal structure analysis. Assuming that isomerization does not occur during the reaction of [P2W17O61Ru III(H2O)]7- with DMSO, the isolated [P 2W17O61RuIII(H2O)] 7- contains the α1-isomer as a main compound with the α2-isomer as a minor compound. Unusual transformation of the α2-isomer of [P2W17O 61]10- to the α1-isomer occurs. Redox behaviors of [α1-P2W17O 61RuII(DMSO)]8- and [α2-P 2W17O61RuII(DMSO)]8- are compared together with Ru(DMSO)-substituted α-Keggin-type heteropolytungstates, [α-XW11O39Ru(DMSO)] n- (X = Si, Ge, and P).

AB - Both α1- and α2-isomers of mono-Ru-substituted Dawson-type heteropolytungstates with a DMSO ligand, [α1-P2W17O61Ru II(DMSO)]8- and [α2-P2W 17O61RuII(DMSO)]8-, are prepared from the α2-isomer of a monolacunary derivative, [α2-P2W17O61]10-. Reaction of [α2-P2W17O61] 10- with Ru(DMSO)4Cl2 under hydrothermal conditions produces [α2-P2W17O 61RuII(DMSO)]8- as a main product together with [α1-P2W17O61Ru II(DMSO)]8-, [PW11O39Ru II(DMSO)]5-, and [P2W18O 62]6- as byproducts. By addition of KCl to the reaction mixture, K8[α2-P2W17O 61RuII(DMSO)] is isolated in a moderate yield. On the other hand, reaction of [α2-P2W17O 61]10- with Ru2(benzene)2Cl 4 under hydrothermal conditions produces an isomeric mixture of [P2W17O61RuIII(H2O)] 7- (α1-isomer/α2-isomer ratio: ca. 8/1) as a main product together with [PW11O39Ru III(H2O)]4- and [P2W 18O62]6- as byproducts. By addition of acetone to the reaction mixture, K7[P2W17O 61RuIII(H2O)] is isolated in a good yield. Reaction of [P2W17O61RuIII(H 2O)]7- with DMSO produces [α1-P 2W17O61RuIII(DMSO)]7- as a main product and [α2-P2W17O 61RuIII(DMSO)]7- as a minor product. By addition of KCl and acetone, the α1-isomer K 8[α1-P2W17O 61RuII(DMSO)] is isolated in a good yield. Both compounds are fully analyzed by CV, NMR (1H, 13C, 31P, and 183W), IR, UV-vis, elemental analysis, mass spectroscopy, and single-crystal structure analysis. Assuming that isomerization does not occur during the reaction of [P2W17O61Ru III(H2O)]7- with DMSO, the isolated [P 2W17O61RuIII(H2O)] 7- contains the α1-isomer as a main compound with the α2-isomer as a minor compound. Unusual transformation of the α2-isomer of [P2W17O 61]10- to the α1-isomer occurs. Redox behaviors of [α1-P2W17O 61RuII(DMSO)]8- and [α2-P 2W17O61RuII(DMSO)]8- are compared together with Ru(DMSO)-substituted α-Keggin-type heteropolytungstates, [α-XW11O39Ru(DMSO)] n- (X = Si, Ge, and P).

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