Synthesis, structure, and dissociation equilibrium of [Co(η5-C5H5) (Se2C6H4)]2, a novel metalladiselenolene complex

Satoru Habe; Teppei Yamada; Takuya Nankawa; Jun Mizutani; Masaki Murata; Hiroshi Nishihara

doi:10.1021/ic025865n

Synthesis, structure, and dissociation equilibrium of [Co(η⁵-C₅H₅) (Se₂C₆H₄)]₂, a novel metalladiselenolene complex

Satoru Habe, Teppei Yamada, Takuya Nankawa, Jun Mizutani, Masaki Murata, Hiroshi Nishihara

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

17 Citations (Scopus)

Abstract

A (phenylenediselenolato)cobalt complex dimer, [Co(η⁵-C₅H₅) (Se₂C₆H₄)]₂ (1), was synthesized by a reaction of carbonyl(η⁵-cyclopentadienyl)diiodocobalt(III) ([Co(η⁵-C₅H₅)I₂(CO)]) with poly(o-diselenobenzene). The structure of 1, determined by single-crystal X-ray crystallography, was found to be located in the space group of P2₁/c (No. 14), with a = 9.3346(5) Å, b = 11.6477(9) Å, c = 10.2179(5) Å, β = 111.491(1)°, and Z = 2. Covalent Co-Se bonds bridge the metal centers. In solution, dimers and monomers coexist at equilibrium. The dissociation equilibrium constant of 1 in solution was evaluated by ¹H NMR spectra at several temperatures between 20 and 80 °C. Dissociation enthalpies/entropies were found to be 50/110, 60/120, and 88 kJ mol^-1/200 J K^-1 mol^-1 in dimethyl sulfoxide-d₆, benzene-d₆, and chloroform-d₁, respectively.

Original language	English
Pages (from-to)	1952-1955
Number of pages	4
Journal	Inorganic Chemistry
Volume	42
Issue number	6
DOIs	https://doi.org/10.1021/ic025865n
Publication status	Published - Mar 24 2003
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Synthesis, structure, and dissociation equilibrium of [Co(η5-C5H5) (Se2C6H4)]2, a novel metalladiselenolene complex",

abstract = "A (phenylenediselenolato)cobalt complex dimer, [Co(η5-C5H5) (Se2C6H4)]2 (1), was synthesized by a reaction of carbonyl(η5-cyclopentadienyl)diiodocobalt(III) ([Co(η5-C5H5)I2(CO)]) with poly(o-diselenobenzene). The structure of 1, determined by single-crystal X-ray crystallography, was found to be located in the space group of P21/c (No. 14), with a = 9.3346(5) {\AA}, b = 11.6477(9) {\AA}, c = 10.2179(5) {\AA}, β = 111.491(1)°, and Z = 2. Covalent Co-Se bonds bridge the metal centers. In solution, dimers and monomers coexist at equilibrium. The dissociation equilibrium constant of 1 in solution was evaluated by 1H NMR spectra at several temperatures between 20 and 80 °C. Dissociation enthalpies/entropies were found to be 50/110, 60/120, and 88 kJ mol-1/200 J K-1 mol-1 in dimethyl sulfoxide-d6, benzene-d6, and chloroform-d1, respectively.",

author = "Satoru Habe and Teppei Yamada and Takuya Nankawa and Jun Mizutani and Masaki Murata and Hiroshi Nishihara",

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T1 - Synthesis, structure, and dissociation equilibrium of [Co(η5-C5H5) (Se2C6H4)]2, a novel metalladiselenolene complex

AU - Habe, Satoru

AU - Yamada, Teppei

AU - Nankawa, Takuya

AU - Mizutani, Jun

AU - Murata, Masaki

AU - Nishihara, Hiroshi

PY - 2003/3/24

Y1 - 2003/3/24

N2 - A (phenylenediselenolato)cobalt complex dimer, [Co(η5-C5H5) (Se2C6H4)]2 (1), was synthesized by a reaction of carbonyl(η5-cyclopentadienyl)diiodocobalt(III) ([Co(η5-C5H5)I2(CO)]) with poly(o-diselenobenzene). The structure of 1, determined by single-crystal X-ray crystallography, was found to be located in the space group of P21/c (No. 14), with a = 9.3346(5) Å, b = 11.6477(9) Å, c = 10.2179(5) Å, β = 111.491(1)°, and Z = 2. Covalent Co-Se bonds bridge the metal centers. In solution, dimers and monomers coexist at equilibrium. The dissociation equilibrium constant of 1 in solution was evaluated by 1H NMR spectra at several temperatures between 20 and 80 °C. Dissociation enthalpies/entropies were found to be 50/110, 60/120, and 88 kJ mol-1/200 J K-1 mol-1 in dimethyl sulfoxide-d6, benzene-d6, and chloroform-d1, respectively.

AB - A (phenylenediselenolato)cobalt complex dimer, [Co(η5-C5H5) (Se2C6H4)]2 (1), was synthesized by a reaction of carbonyl(η5-cyclopentadienyl)diiodocobalt(III) ([Co(η5-C5H5)I2(CO)]) with poly(o-diselenobenzene). The structure of 1, determined by single-crystal X-ray crystallography, was found to be located in the space group of P21/c (No. 14), with a = 9.3346(5) Å, b = 11.6477(9) Å, c = 10.2179(5) Å, β = 111.491(1)°, and Z = 2. Covalent Co-Se bonds bridge the metal centers. In solution, dimers and monomers coexist at equilibrium. The dissociation equilibrium constant of 1 in solution was evaluated by 1H NMR spectra at several temperatures between 20 and 80 °C. Dissociation enthalpies/entropies were found to be 50/110, 60/120, and 88 kJ mol-1/200 J K-1 mol-1 in dimethyl sulfoxide-d6, benzene-d6, and chloroform-d1, respectively.

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Synthesis, structure, and dissociation equilibrium of [Co(η⁵-C₅H₅) (Se₂C₆H₄)]₂, a novel metalladiselenolene complex

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