Cobalt(II) phosphine complexes stable in aqueous solution

Spectroscopic and kinetic evidence for low-spin Co(II)P6 and Co(II)P3S3 with tripodal 1,1,1-tris(dimethylphosphinomethyl) ethane

Satoshi Iwatsuki, Hiroo Kato, Kenji Obeyama, Shigenobu Funahashi, Nobuyoshi Koshino, Kazuo Kashiwabara, Takayoshi Suzuki, Hideo D. Takagi

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Co(II) species produced by the controlled potential electrochemical reduction of Co(III)P3S3. and Co(III)P6 complexes with 1,4,7-trithiacyclononane and tripodal 1,1,1-tris(dimethylphosphinomethyl)ethane in aqueous solution were characterized at ambient temperature by the EPR and spectrophotometric methods: The Co(II)P6 and Co(II)P3S3 species are in the low-spin t(2g)/6e(g)/1 state with large Jahn-Teller distortion. Kinetic studies of the redox reactions involving these Co(III)/(II) species revealed that the electron self-exchange reactions for the Co(III)/(II) couples are very fast (k(ex) ~ 104 dm3 mol-1 s-1), which is consistent with the results for other low-spin/low-spin Co(III)/(II) couples. It was concluded that the nephelauxetic effect of the P donor atom stabilizes the low-spin state in Co(II). (C) 2000 Elsevier Science S.A.

Original languageEnglish
Pages (from-to)501-504
Number of pages4
JournalInorganic Chemistry Communications
Volume3
Issue number10
DOIs
Publication statusPublished - 2000
Externally publishedYes

Fingerprint

phosphine
Jahn-Teller effect
Ethane
Redox reactions
Cobalt
phosphines
ethane
Oxidation-Reduction
Paramagnetic resonance
cobalt
Electrons
aqueous solutions
Atoms
Kinetics
Temperature
kinetics
ambient temperature
trithiacyclononane

Keywords

  • Cobalt(II)
  • Electron transfer
  • EPR study
  • Kinetics
  • Spin state

ASJC Scopus subject areas

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

Cite this

Cobalt(II) phosphine complexes stable in aqueous solution : Spectroscopic and kinetic evidence for low-spin Co(II)P6 and Co(II)P3S3 with tripodal 1,1,1-tris(dimethylphosphinomethyl) ethane. / Iwatsuki, Satoshi; Kato, Hiroo; Obeyama, Kenji; Funahashi, Shigenobu; Koshino, Nobuyoshi; Kashiwabara, Kazuo; Suzuki, Takayoshi; Takagi, Hideo D.

In: Inorganic Chemistry Communications, Vol. 3, No. 10, 2000, p. 501-504.

Research output: Contribution to journalArticle

Iwatsuki, Satoshi ; Kato, Hiroo ; Obeyama, Kenji ; Funahashi, Shigenobu ; Koshino, Nobuyoshi ; Kashiwabara, Kazuo ; Suzuki, Takayoshi ; Takagi, Hideo D. / Cobalt(II) phosphine complexes stable in aqueous solution : Spectroscopic and kinetic evidence for low-spin Co(II)P6 and Co(II)P3S3 with tripodal 1,1,1-tris(dimethylphosphinomethyl) ethane. In: Inorganic Chemistry Communications. 2000 ; Vol. 3, No. 10. pp. 501-504.
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T1 - Cobalt(II) phosphine complexes stable in aqueous solution

T2 - Spectroscopic and kinetic evidence for low-spin Co(II)P6 and Co(II)P3S3 with tripodal 1,1,1-tris(dimethylphosphinomethyl) ethane

AU - Iwatsuki, Satoshi

AU - Kato, Hiroo

AU - Obeyama, Kenji

AU - Funahashi, Shigenobu

AU - Koshino, Nobuyoshi

AU - Kashiwabara, Kazuo

AU - Suzuki, Takayoshi

AU - Takagi, Hideo D.

PY - 2000

Y1 - 2000

N2 - Co(II) species produced by the controlled potential electrochemical reduction of Co(III)P3S3. and Co(III)P6 complexes with 1,4,7-trithiacyclononane and tripodal 1,1,1-tris(dimethylphosphinomethyl)ethane in aqueous solution were characterized at ambient temperature by the EPR and spectrophotometric methods: The Co(II)P6 and Co(II)P3S3 species are in the low-spin t(2g)/6e(g)/1 state with large Jahn-Teller distortion. Kinetic studies of the redox reactions involving these Co(III)/(II) species revealed that the electron self-exchange reactions for the Co(III)/(II) couples are very fast (k(ex) ~ 104 dm3 mol-1 s-1), which is consistent with the results for other low-spin/low-spin Co(III)/(II) couples. It was concluded that the nephelauxetic effect of the P donor atom stabilizes the low-spin state in Co(II). (C) 2000 Elsevier Science S.A.

AB - Co(II) species produced by the controlled potential electrochemical reduction of Co(III)P3S3. and Co(III)P6 complexes with 1,4,7-trithiacyclononane and tripodal 1,1,1-tris(dimethylphosphinomethyl)ethane in aqueous solution were characterized at ambient temperature by the EPR and spectrophotometric methods: The Co(II)P6 and Co(II)P3S3 species are in the low-spin t(2g)/6e(g)/1 state with large Jahn-Teller distortion. Kinetic studies of the redox reactions involving these Co(III)/(II) species revealed that the electron self-exchange reactions for the Co(III)/(II) couples are very fast (k(ex) ~ 104 dm3 mol-1 s-1), which is consistent with the results for other low-spin/low-spin Co(III)/(II) couples. It was concluded that the nephelauxetic effect of the P donor atom stabilizes the low-spin state in Co(II). (C) 2000 Elsevier Science S.A.

KW - Cobalt(II)

KW - Electron transfer

KW - EPR study

KW - Kinetics

KW - Spin state

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