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

doi:10.1016/S1387-7003(00)00134-9

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 journal › Article › peer-review

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 language	English
Pages (from-to)	501-504
Number of pages	4
Journal	Inorganic Chemistry Communications
Volume	3
Issue number	10
DOIs	https://doi.org/10.1016/S1387-7003(00)00134-9
Publication status	Published - 2000
Externally published	Yes

Keywords

Cobalt(II)
EPR study
Electron transfer
Kinetics
Spin state

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S1387-7003(00)00134-9

Cite this

Iwatsuki, S., Kato, H., Obeyama, K., Funahashi, S., Koshino, N., Kashiwabara, K., Suzuki, T., & Takagi, H. D. (2000). 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. Inorganic Chemistry Communications, 3(10), 501-504. https://doi.org/10.1016/S1387-7003(00)00134-9

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 et al.

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

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

Iwatsuki, S, Kato, H, Obeyama, K, Funahashi, S, Koshino, N, Kashiwabara, K, Suzuki, T & Takagi, HD 2000, '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', Inorganic Chemistry Communications, vol. 3, no. 10, pp. 501-504. https://doi.org/10.1016/S1387-7003(00)00134-9

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title = "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",

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.",

keywords = "Cobalt(II), EPR study, Electron transfer, Kinetics, Spin state",

author = "Satoshi Iwatsuki and Hiroo Kato and Kenji Obeyama and Shigenobu Funahashi and Nobuyoshi Koshino and Kazuo Kashiwabara and Takayoshi Suzuki and Takagi, {Hideo D.}",

note = "Funding Information: This research was partly supported by the Grants-in-Aid for Scientific Research (Grant Nos. 05453042, 07554061, 07504003, 11640562 and 10440193) from the Ministry of Education, Science and Culture of Japan, and by the Kurata Foundations (Hitachi Corp.).",

year = "2000",

doi = "10.1016/S1387-7003(00)00134-9",

language = "English",

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pages = "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.

N1 - Funding Information: This research was partly supported by the Grants-in-Aid for Scientific Research (Grant Nos. 05453042, 07554061, 07504003, 11640562 and 10440193) from the Ministry of Education, Science and Culture of Japan, and by the Kurata Foundations (Hitachi Corp.).

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 - EPR study

KW - Electron transfer

KW - Kinetics

KW - Spin state

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