Redox Conversion of Cobalt(II)-Diselenide to Cobalt(III)-Selenolate Compounds: Comparison with Their Sulfur Analogs

Christian Marvelous; Lucas de Azevedo Santos; Maxime A. Siegler; Célia Fonseca Guerra; Elisabeth Bouwman

doi:10.1002/ejic.202200445

Redox Conversion of Cobalt(II)-Diselenide to Cobalt(III)-Selenolate Compounds: Comparison with Their Sulfur Analogs

Christian Marvelous, Lucas de Azevedo Santos, Maxime A. Siegler, Célia Fonseca Guerra^*, Elisabeth Bouwman

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The synthesis of the selenium-based ligand L¹SeSeL¹ (2,2’-diselanediylbis(N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) is described along with its reactivity with cobalt(II) salts. The cobalt(II)-diselenide complex [Co₂(L¹SeSeL¹)Cl₄] was obtained in good yield, and its spectroscopic properties closely resemble that of its sulfur analog. Reaction of L¹SeSeL¹ with Co(II) thiocyanate results in the formation of the cobalt(III) compound [Co(L¹Se)(NCS)₂], similar to reaction of L¹SSL¹. The redox-conversion reactions from the Co(II)-diselenide compound [Co(L¹SeSeL¹)Cl₄] using external triggers such as removal of the halide ions or the addition of the strong-field ligand 8-quinolinolate resulted in good yields of the Co(III)-selenolate complexes [Co(L¹Se)(MeCN)₂](SbF₆)₂ and [Co(L¹Se)(quin)]Cl. Our computational studies show that the ligand-field splitting energy of the selenium compounds is smaller than their sulfur analogs, indicating that redox-conversion of cobalt(II)-diselenide to cobalt(III)-selenolate complexes may be more arduous than that for the related sulfur compounds.

Original language	English
Article number	e202200445
Pages (from-to)	1-9
Number of pages	9
Journal	European Journal of Inorganic Chemistry
Volume	2022
Issue number	33
Early online date	14 Sept 2022
DOIs	https://doi.org/10.1002/ejic.202200445
Publication status	Published - 25 Nov 2022

Bibliographical note

Funding Information:
The authors would like to thank the Key Laboratory of Intelligent Perception and Image Understanding of Ministry of Education of Xidian University for help in providing the test datasets. This work was supported by the National Natural Science Foundation of China (Grant No. 61806163 and No. 61773314), in part by the Natural Science Basic Research Plan in the Shaanxi Province of China under Grant 2019‐SQ‐359 and Grant 2019‐SQ‐520, in part by the Scientific Research Program Founded by Shaanxi Provincial Education Department of China under Grant 18JK0551 and 18JK0562.

Publisher Copyright:
© 2022 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.

Funding

The authors would like to thank the Key Laboratory of Intelligent Perception and Image Understanding of Ministry of Education of Xidian University for help in providing the test datasets. This work was supported by the National Natural Science Foundation of China (Grant No. 61806163 and No. 61773314), in part by the Natural Science Basic Research Plan in the Shaanxi Province of China under Grant 2019‐SQ‐359 and Grant 2019‐SQ‐520, in part by the Scientific Research Program Founded by Shaanxi Provincial Education Department of China under Grant 18JK0551 and 18JK0562.

Funders	Funder number
National Natural Science Foundation of China	61773314, 61806163
National Natural Science Foundation of China
Education Department of Shaanxi Province	18JK0551, 18JK0562
Education Department of Shaanxi Province
Natural Science Basic Research Program of Shaanxi Province	2019‐SQ‐520, 2019‐SQ‐359
Natural Science Basic Research Program of Shaanxi Province

Keywords

Chalcogens
Cobalt
Density functional calculations
Redox chemistry
Selenium

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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title = "Redox Conversion of Cobalt(II)-Diselenide to Cobalt(III)-Selenolate Compounds: Comparison with Their Sulfur Analogs",

abstract = "The synthesis of the selenium-based ligand L1SeSeL1 (2,2{\textquoteright}-diselanediylbis(N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) is described along with its reactivity with cobalt(II) salts. The cobalt(II)-diselenide complex [Co2(L1SeSeL1)Cl4] was obtained in good yield, and its spectroscopic properties closely resemble that of its sulfur analog. Reaction of L1SeSeL1 with Co(II) thiocyanate results in the formation of the cobalt(III) compound [Co(L1Se)(NCS)2], similar to reaction of L1SSL1. The redox-conversion reactions from the Co(II)-diselenide compound [Co(L1SeSeL1)Cl4] using external triggers such as removal of the halide ions or the addition of the strong-field ligand 8-quinolinolate resulted in good yields of the Co(III)-selenolate complexes [Co(L1Se)(MeCN)2](SbF6)2 and [Co(L1Se)(quin)]Cl. Our computational studies show that the ligand-field splitting energy of the selenium compounds is smaller than their sulfur analogs, indicating that redox-conversion of cobalt(II)-diselenide to cobalt(III)-selenolate complexes may be more arduous than that for the related sulfur compounds.",

keywords = "Chalcogens, Cobalt, Density functional calculations, Redox chemistry, Selenium",

author = "Christian Marvelous and {de Azevedo Santos}, Lucas and Siegler, {Maxime A.} and {Fonseca Guerra}, C{\'e}lia and Elisabeth Bouwman",

note = "Funding Information: The authors would like to thank the Key Laboratory of Intelligent Perception and Image Understanding of Ministry of Education of Xidian University for help in providing the test datasets. This work was supported by the National Natural Science Foundation of China (Grant No. 61806163 and No. 61773314), in part by the Natural Science Basic Research Plan in the Shaanxi Province of China under Grant 2019‐SQ‐359 and Grant 2019‐SQ‐520, in part by the Scientific Research Program Founded by Shaanxi Provincial Education Department of China under Grant 18JK0551 and 18JK0562. Publisher Copyright: {\textcopyright} 2022 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.",

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T1 - Redox Conversion of Cobalt(II)-Diselenide to Cobalt(III)-Selenolate Compounds

T2 - Comparison with Their Sulfur Analogs

AU - Marvelous, Christian

AU - de Azevedo Santos, Lucas

AU - Siegler, Maxime A.

AU - Fonseca Guerra, Célia

AU - Bouwman, Elisabeth

N1 - Funding Information: The authors would like to thank the Key Laboratory of Intelligent Perception and Image Understanding of Ministry of Education of Xidian University for help in providing the test datasets. This work was supported by the National Natural Science Foundation of China (Grant No. 61806163 and No. 61773314), in part by the Natural Science Basic Research Plan in the Shaanxi Province of China under Grant 2019‐SQ‐359 and Grant 2019‐SQ‐520, in part by the Scientific Research Program Founded by Shaanxi Provincial Education Department of China under Grant 18JK0551 and 18JK0562. Publisher Copyright: © 2022 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.

PY - 2022/11/25

Y1 - 2022/11/25

N2 - The synthesis of the selenium-based ligand L1SeSeL1 (2,2’-diselanediylbis(N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) is described along with its reactivity with cobalt(II) salts. The cobalt(II)-diselenide complex [Co2(L1SeSeL1)Cl4] was obtained in good yield, and its spectroscopic properties closely resemble that of its sulfur analog. Reaction of L1SeSeL1 with Co(II) thiocyanate results in the formation of the cobalt(III) compound [Co(L1Se)(NCS)2], similar to reaction of L1SSL1. The redox-conversion reactions from the Co(II)-diselenide compound [Co(L1SeSeL1)Cl4] using external triggers such as removal of the halide ions or the addition of the strong-field ligand 8-quinolinolate resulted in good yields of the Co(III)-selenolate complexes [Co(L1Se)(MeCN)2](SbF6)2 and [Co(L1Se)(quin)]Cl. Our computational studies show that the ligand-field splitting energy of the selenium compounds is smaller than their sulfur analogs, indicating that redox-conversion of cobalt(II)-diselenide to cobalt(III)-selenolate complexes may be more arduous than that for the related sulfur compounds.

AB - The synthesis of the selenium-based ligand L1SeSeL1 (2,2’-diselanediylbis(N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) is described along with its reactivity with cobalt(II) salts. The cobalt(II)-diselenide complex [Co2(L1SeSeL1)Cl4] was obtained in good yield, and its spectroscopic properties closely resemble that of its sulfur analog. Reaction of L1SeSeL1 with Co(II) thiocyanate results in the formation of the cobalt(III) compound [Co(L1Se)(NCS)2], similar to reaction of L1SSL1. The redox-conversion reactions from the Co(II)-diselenide compound [Co(L1SeSeL1)Cl4] using external triggers such as removal of the halide ions or the addition of the strong-field ligand 8-quinolinolate resulted in good yields of the Co(III)-selenolate complexes [Co(L1Se)(MeCN)2](SbF6)2 and [Co(L1Se)(quin)]Cl. Our computational studies show that the ligand-field splitting energy of the selenium compounds is smaller than their sulfur analogs, indicating that redox-conversion of cobalt(II)-diselenide to cobalt(III)-selenolate complexes may be more arduous than that for the related sulfur compounds.

KW - Chalcogens

KW - Cobalt

KW - Density functional calculations

KW - Redox chemistry

KW - Selenium

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JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

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ER -

Redox Conversion of Cobalt(II)-Diselenide to Cobalt(III)-Selenolate Compounds: Comparison with Their Sulfur Analogs

Abstract

Bibliographical note

Funding

Keywords

UN SDGs

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