The first osmium(II), ruthenium(II) and iron(II) complexes of [3n]cyclophanes (n = 2-4): Synthesis and electrochemical study

Teizi Satou, Ko Takehara, Mihoko Hirakida, Youichi Sakamoto, Hiroyuki Takemura, Hirokazu Miura, Mie Tomonou, Teruo Shinmyozu

Research output: Contribution to journalArticle

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Abstract

6-C6H6)(η6-[3 n]Cyclophane)Ru(II) [BF4]2 and corresponding Os(II) [PF6]2, as well as bis(η5-C5H5)(η66-[3n]cyclophane)Fe(II)Fe(II) [PF6]2 ([3n]cyclophane = [32](1,4)cyclophane 2, [33](1,3,5)cyclophane 3, [34](1,2,3,5)cyclophane 4, [34](1,2,4,5)cyclophane 5) have been synthesized and characterized. The complexation shifts of the 1H-NMR signals of the metal-bound aromatic protons (Hb) are ca. 0.5-0.7 and 0.1-0.4 ppm for Fe(II) and Ru(II) complexes, respectively, whereas those of Os(II) complexes are ca. -0.2-0.1 ppm. The complexation shifts of the 13C-NMR signals of the tertiary aromatic carbons of the metal-bound benzene ring are ca. 39-42 and 45-50 ppm for Ru(II) and Os(II) complexes, respectively. Thus the 1H- and 13C-NMR chemical shifts of the metal-bound aromatic hydrogens and carbons are strongly influenced by the anisotropy effect of the metal. The Ru(II) complexes showed electrochemically reversible responses. In the case of Os(II) complexes, a well-defined cathodic peak was also observed, but the rising portion of the corresponding anodic peak was somewhat deviated from the ordinary CV profile. In both cases, the redox process was attributed to the two-electron one-step mechanism, M(II) ⇌ M(0) (M = Ru and Os). An analysis of the redox properties of the Ru(II) and Os(II) complexes suggested that the Os(II)[34](1,2,4,5)cyclophane complex would be the most suitable subunit of an anticipated one-dimensional organometallic polymer.

Original languageEnglish
Pages (from-to)58-68
Number of pages11
JournalJournal of Organometallic Chemistry
Volume577
Issue number1
DOIs
Publication statusPublished - Mar 27 1999

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Osmium
Ruthenium
osmium
ruthenium
Iron
Metals
iron
Nuclear magnetic resonance
synthesis
Complexation
metals
nuclear magnetic resonance
Oxidation-Reduction
organometallic polymers
Carbon
carbon
shift
Anisotropy
Chemical shift
Organometallics

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

The first osmium(II), ruthenium(II) and iron(II) complexes of [3n]cyclophanes (n = 2-4) : Synthesis and electrochemical study. / Satou, Teizi; Takehara, Ko; Hirakida, Mihoko; Sakamoto, Youichi; Takemura, Hiroyuki; Miura, Hirokazu; Tomonou, Mie; Shinmyozu, Teruo.

In: Journal of Organometallic Chemistry, Vol. 577, No. 1, 27.03.1999, p. 58-68.

Research output: Contribution to journalArticle

Satou, T, Takehara, K, Hirakida, M, Sakamoto, Y, Takemura, H, Miura, H, Tomonou, M & Shinmyozu, T 1999, 'The first osmium(II), ruthenium(II) and iron(II) complexes of [3n]cyclophanes (n = 2-4): Synthesis and electrochemical study', Journal of Organometallic Chemistry, vol. 577, no. 1, pp. 58-68. https://doi.org/10.1016/S0022-328X(98)01025-0
Satou, Teizi ; Takehara, Ko ; Hirakida, Mihoko ; Sakamoto, Youichi ; Takemura, Hiroyuki ; Miura, Hirokazu ; Tomonou, Mie ; Shinmyozu, Teruo. / The first osmium(II), ruthenium(II) and iron(II) complexes of [3n]cyclophanes (n = 2-4) : Synthesis and electrochemical study. In: Journal of Organometallic Chemistry. 1999 ; Vol. 577, No. 1. pp. 58-68.
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abstract = "(η6-C6H6)(η6-[3 n]Cyclophane)Ru(II) [BF4]2 and corresponding Os(II) [PF6]2, as well as bis(η5-C5H5)(η6,η 6-[3n]cyclophane)Fe(II)Fe(II) [PF6]2 ([3n]cyclophane = [32](1,4)cyclophane 2, [33](1,3,5)cyclophane 3, [34](1,2,3,5)cyclophane 4, [34](1,2,4,5)cyclophane 5) have been synthesized and characterized. The complexation shifts of the 1H-NMR signals of the metal-bound aromatic protons (Hb) are ca. 0.5-0.7 and 0.1-0.4 ppm for Fe(II) and Ru(II) complexes, respectively, whereas those of Os(II) complexes are ca. -0.2-0.1 ppm. The complexation shifts of the 13C-NMR signals of the tertiary aromatic carbons of the metal-bound benzene ring are ca. 39-42 and 45-50 ppm for Ru(II) and Os(II) complexes, respectively. Thus the 1H- and 13C-NMR chemical shifts of the metal-bound aromatic hydrogens and carbons are strongly influenced by the anisotropy effect of the metal. The Ru(II) complexes showed electrochemically reversible responses. In the case of Os(II) complexes, a well-defined cathodic peak was also observed, but the rising portion of the corresponding anodic peak was somewhat deviated from the ordinary CV profile. In both cases, the redox process was attributed to the two-electron one-step mechanism, M(II) ⇌ M(0) (M = Ru and Os). An analysis of the redox properties of the Ru(II) and Os(II) complexes suggested that the Os(II)[34](1,2,4,5)cyclophane complex would be the most suitable subunit of an anticipated one-dimensional organometallic polymer.",
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T1 - The first osmium(II), ruthenium(II) and iron(II) complexes of [3n]cyclophanes (n = 2-4)

T2 - Synthesis and electrochemical study

AU - Satou, Teizi

AU - Takehara, Ko

AU - Hirakida, Mihoko

AU - Sakamoto, Youichi

AU - Takemura, Hiroyuki

AU - Miura, Hirokazu

AU - Tomonou, Mie

AU - Shinmyozu, Teruo

PY - 1999/3/27

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N2 - (η6-C6H6)(η6-[3 n]Cyclophane)Ru(II) [BF4]2 and corresponding Os(II) [PF6]2, as well as bis(η5-C5H5)(η6,η 6-[3n]cyclophane)Fe(II)Fe(II) [PF6]2 ([3n]cyclophane = [32](1,4)cyclophane 2, [33](1,3,5)cyclophane 3, [34](1,2,3,5)cyclophane 4, [34](1,2,4,5)cyclophane 5) have been synthesized and characterized. The complexation shifts of the 1H-NMR signals of the metal-bound aromatic protons (Hb) are ca. 0.5-0.7 and 0.1-0.4 ppm for Fe(II) and Ru(II) complexes, respectively, whereas those of Os(II) complexes are ca. -0.2-0.1 ppm. The complexation shifts of the 13C-NMR signals of the tertiary aromatic carbons of the metal-bound benzene ring are ca. 39-42 and 45-50 ppm for Ru(II) and Os(II) complexes, respectively. Thus the 1H- and 13C-NMR chemical shifts of the metal-bound aromatic hydrogens and carbons are strongly influenced by the anisotropy effect of the metal. The Ru(II) complexes showed electrochemically reversible responses. In the case of Os(II) complexes, a well-defined cathodic peak was also observed, but the rising portion of the corresponding anodic peak was somewhat deviated from the ordinary CV profile. In both cases, the redox process was attributed to the two-electron one-step mechanism, M(II) ⇌ M(0) (M = Ru and Os). An analysis of the redox properties of the Ru(II) and Os(II) complexes suggested that the Os(II)[34](1,2,4,5)cyclophane complex would be the most suitable subunit of an anticipated one-dimensional organometallic polymer.

AB - (η6-C6H6)(η6-[3 n]Cyclophane)Ru(II) [BF4]2 and corresponding Os(II) [PF6]2, as well as bis(η5-C5H5)(η6,η 6-[3n]cyclophane)Fe(II)Fe(II) [PF6]2 ([3n]cyclophane = [32](1,4)cyclophane 2, [33](1,3,5)cyclophane 3, [34](1,2,3,5)cyclophane 4, [34](1,2,4,5)cyclophane 5) have been synthesized and characterized. The complexation shifts of the 1H-NMR signals of the metal-bound aromatic protons (Hb) are ca. 0.5-0.7 and 0.1-0.4 ppm for Fe(II) and Ru(II) complexes, respectively, whereas those of Os(II) complexes are ca. -0.2-0.1 ppm. The complexation shifts of the 13C-NMR signals of the tertiary aromatic carbons of the metal-bound benzene ring are ca. 39-42 and 45-50 ppm for Ru(II) and Os(II) complexes, respectively. Thus the 1H- and 13C-NMR chemical shifts of the metal-bound aromatic hydrogens and carbons are strongly influenced by the anisotropy effect of the metal. The Ru(II) complexes showed electrochemically reversible responses. In the case of Os(II) complexes, a well-defined cathodic peak was also observed, but the rising portion of the corresponding anodic peak was somewhat deviated from the ordinary CV profile. In both cases, the redox process was attributed to the two-electron one-step mechanism, M(II) ⇌ M(0) (M = Ru and Os). An analysis of the redox properties of the Ru(II) and Os(II) complexes suggested that the Os(II)[34](1,2,4,5)cyclophane complex would be the most suitable subunit of an anticipated one-dimensional organometallic polymer.

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