Synthesis, Crystal Structures, Electronic Spectra, and Magnetic Properties of Thiolato-Bridged Trinuclear Cobalt(II) Complexes with N, N, S-Tridentate Thiolate Ligands

Masahiro Mikuriya; Atsushi Fujita; Takanori Kotera; Daisuke Yoshioka; Hiroshi Sakiyama; Makoto Handa; Motohiro Tsuboi

doi:10.26877/asset.v3i1.8352

Synthesis, Crystal Structures, Electronic Spectra, and Magnetic Properties of Thiolato-Bridged Trinuclear Cobalt(II) Complexes with N, N, S-Tridentate Thiolate Ligands

Masahiro Mikuriya, Atsushi Fujita, Takanori Kotera, Daisuke Yoshioka, Hiroshi Sakiyama, Makoto Handa, Motohiro Tsuboi

Abstract

New trinuclear Co^II complexes, [{Co(apaet)₂}₂Co]X₂ (apaet^– = 2-[(3-aminopropyl)amino]ethanethiolato; X = SCN (1), ClO₄ (2), NO₃(3), Cl (4), Br (5), I (6)) and [{Co(apampt)₂}₂Co]X₂ (apampt^– = 1-[(3-aminopropyl)amino]-2-methylpropane-2-thiolato; X = NO₃(7), ClO₄ (8), Cl (9), Br (10), I (11)), and mononuclear Co^III complexes, [Co(apaet)₂]X (X = ClO₄ (12), NO₃(13)), were synthesized. Single-crystal X-ray crystallography of 1 and 7 confirmed that the trinuclear complexes have a linear arrangement of octahedral Co^IIS₂N₄-tetrahedral Co^IIS₄-octahedral Co^IIS₂N₄ chromophores where two thiolate ligands are coordinated to each terminal Co atom in a mer coordination mode and the two thiolato S atoms are further bound to the central Co atom, which is consistent with the electronic spectra and antiferromagnetic properties

Keywords

thiolato complex; cobalt complex; mononuclear Co(III) complex; trinuclear Co(II) complex

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References

I. G. Dance, "The Structural Chemistry of Metal Thiolate Complexes," Polyhedron, vol. 5, pp. 1037-1104, 1986. hahaha

P. J. Blower and J. R. Dilworth, "Thiolato-complexes of the Transition Metals," Coord. Chem. Rev., vol. 76, pp. 769-788, 1991. https://doi.org/10.1016/0010-8545(87)85003-8

B. Krebs and G. Henkel, "Transition-Metal Thiolates: From Molecular Fragments of Sulfidic Solids to Models for Active Centers in Biomolecules," Angew. Chem. Int. Ed. Engl., vol. 30, pp.769-788, 1991. https://doi.org/10.1002/anie.199107691

J. R. Dilworth and J. Hu, “Complexes of Sterically Hindered Thiolate Ligands," Adv. Inorg. Chem., vol. 40, pp. 411–459, 1993. https://doi.org/10.1016/S0898-8838(08)60187-7

A. C. Marr, D. J. E. Spencer, and M. Schröder, "Structural mimics for the active site of [NiFe] hydrogenase," Coord. Chem. Rev., vol. 219-221, pp. 1055–1074, 2001. https://doi.org/10.1016/S0010-8545(01)00396-4

T. Konno, "Aggregation of Octahedral Thiolato Complexes by Forming Sulfur-Bridged Structures with Transition Metal Ions," Bull. Chem. Soc. Jpn., vol. 77, pp. 627-649, 2004. https://doi.org/10.1246/bcsj.77.627

H. Fleischer, “Structural chemistry of complexes of (n - 1)d10 nsm metal ions with b-N-donor substituted thiolate ligands (m = 0, 2),” Coord. Chem. Rev., vol. 249, pp. 799–827, 2005. https://doi.org/10.1016/j.ccr.2004.08.024

M. H. Asim, M. Ijaz, A. C. Rosch, and A. Bernkop-Schnurch,"Thiolated cyclodextrins: New perspectives for old excipients," Coord. Chem. Rev., vol. 420, p. 213433, 2020. https://doi.org/10.1016/j.ccr.2020.213433

M. Mikuriya, K. Miyoshi, S. Kurano, J. Taguchi, T. Kotera, and D. Yoshioka, "Synthesis and Crystal Structure of 1,4,7-Tris(2-mercaptoethyl)-1,4,7-triazacyclononane," X-ray Struct. Anal. Online, vol. 31, pp. 59-60, 2015. https://doi.org/10.2116/xraystruct.31.59

M. Mikuriya, S. Kida, S. Ueno, and I. Murase, "Crystal and Molecular Structure of a Triply-thiolate-bridged Binuclear Cobalt(III) Complex, [Co2{SCH(CH2CH2NH2)2}3](ClO4)2·H2O," Bull. Chem. Soc. Jpn., vol. 58, pp. 1857-1858, 1985. https://doi.org/10.1246/bcsj.58.1857

M. Mikuriya, S. Kida, and I. Murase, "Crystal and Molecular Structure of a Thiolate-bridged Binuclear Nickel(II) Complex, [Ni2{SCH(CH2CH2NH2)2}2]Br2," Bull. Chem. Soc. Jpn., vol. 60, pp. 1180-1182, 1987. https://doi.org/10.1246/bcsj.60.1180

M. Handa, M. Mikuriya, J. Z. Zhuang, H. Okawa, and S. Kida, "Synthesis, Properties, and Crystal Structure of Binuclear Nickel(II) and Palladium(II) Complexes of Tridentate Thiolic Ligands with NNS-Donor Set," Bull. Chem. Soc. Jpn., vol. 61, pp. 3883-3887, 1988. https://doi.org/10.1246/bcsj.61.3883

M. Mikuriya, S. Shigematsu, M. Handa, and T. Kohzuma, "Redox properties of thiolate-bridged binuclear nickel(II) complexes and correlation of their electronic spectra, Transition Met. Chem., vol. 16, pp. 532-534, 1991. https://doi.org/10.1007/BF01024325

M. Mikuriya, F. Adachi, H. Iwasawa, M. Handa, M. Koikawa, and H. Okawa, "A novel thiolate-bridged polynuclear manganese(II) complex with 2-[2-(2-pyridyl)ethylamino]ethanethiol," Inorg. Chim. Acta,, vol. 179, pp. 3-5, 1991. https://doi.org/10.1016/S0020-1693(00)85364-5

M. Mikuriya, M. Handa, S. Shigematsu, S. Funaki, F. Adachi, and H. Okawa, "Thiolate-Bridged Binuclear Nickel(II) Complexes with a Mixed-Spin State," Bull. Chem. Soc. Jpn., vol. 65, pp. 512-516, 1992. https://doi.org/10.1246/bcsj.65.512

M. Mikuriya, M. Handa, S. Shigematsu, S. Funaki, T. Fujii, H. Okawa, K. Toriumi, T. Koshiba, and H. Terauchi, "Synthesis and Characterization of Thiolate-Bridged Dinuclear Nickel(II) Complexes with Thioether Pendant Arms," Bull. Chem. Soc. Jpn., vol. 66, pp. 1104-1110, 1993. https://doi.org/10.1246/bcsj.66.1104

M. Mikuriya, F. Adachi, H. Iwasawa, M. Handa, M. Koikawa, and H. Okawa, "Syntheses and Characterization of Thiolate-Bridged Manganese(II) Complexes with NNS-Tridentate Thiolic Ligands," Bull. Chem. Soc. Jpn., vol.67, pp. 3263-3270, 1994. https://doi.org/10.1246/bcsj.67.3263

M. Mikuriya, T. Kotera, F. Adachi, M. Handa, M. Koikawa, and H. Okawa, "Synthesis and Structural Characterization of Dinuclear and Trinuclear Iron(II) Complexes of Tridentate Thiolic Ligands with an NNS Donor Set," Bull. Chem. Soc. Jpn., vol. 68, pp. 574-580, 1995. https://doi.org/10.1246/bcsj.68.574

M. Mikuriya, H. Tsutsumi, R. Nukada, M. Handa, and Y. Sayama, "Synthesis and Characterization of Thiolato-Bridged Trinuclear Heterometal Complexes with 2-[(3-Aminopropyl)amino]ethanethiol," Bull. Chem. Soc. Jpn., vol. 69, pp. 3489-3498, 1996. https://doi.org/10.1246/bcsj.69.3489

T. Kawahashi, H. Tsutsumi, and M. Mikuriya, "A Novel Tetranuclear Palladium(II) Complex with 2-[(3-Aminopropyl)amino]ethanethiol," Polyhedron, vol. 15, pp. 169-171, 1996. https://doi.org/10.1016/0277-5387(95)00227-J

T. Kawahashi, M. Mikuriya, R. Nukada, and J.–W. Lim, "Synthesis and Structural Characterization of Thiolato-Bridged Tetranuclear Palladium(II) Complexes with N,N,S-Tridentate Ligands," Bull. Chem. Soc. Jpn., vol. 74, pp. 323-329, 2001. https://doi.org/10.1246/bcsj.74.323

M. Mikuriya, J. Xiao, S. Ikemi, T. Kawahashi, and H. Tsutsumi, "Synthesis and Structural Characterization of Thiolato-Bridged Zinc(II) Complexes with NNS-Tridentate Ligands," Bull. Chem. Soc. Jpn., vol. 71, pp. 2161-2168, 1998. https://doi.org/10.1246/bcsj.71.2161

M. Mikuriya and T. Kotera, "Novel Thiolato-Bridged Tetranuclear Manganese(II) and Iron(II) Complexes with Adamantane-like Cores," Chem. Lett., pp. 971-972, 1998. https://doi.org/10.1246/cl.1998.971

M. Mikuriya, J. Xiao, S. Ikemi, T. Kawahashi, H. Tsutsumi, A. Nakasone, and J. -W. Lim, "Synthesis and characterization of thiolato-bridged cadmium(II) complexes with NNS-chelating thiolic ligands," Inorg. Chim. Acta, vol. 312, pp. 183-187, 2001. https://doi.org/10.1016/S0020-1693(00)00364-9

T. Kotera and M. Mikuriya, "Thiolato-Bridged Hexanuclear CuICuII Mixed-Valence Complex," Chem. Lett. vol. 31, pp. 654-655, 2002. https://doi.org/10.1246/cl.2002.654

T. Kotera, A. Fujita, M. Mikuriya, and M. Handa, "Thiolao-bridged copper complexes with N,N,S-tridentate ligands," Materials Science (Poland), vol. 21, pp. 171-179, 2003.

T. Kotera, A. Fujita, M. Mikuriya, H. Tsutsumi, and M. Handa, "Cobalt complexes with 2-[(3-aminopropyl)amino]ethanethiol," Inorg. Chem. Commun., vol. 6, pp. 322-324, 2003. https://doi.org/10.1016/S1387-7003(02)00755-4

T. Kotera, T. Sugimoto, and M. Mikuriya, "A thiolato-bridged Octanuclear Copper(I,II) Mixed-Valence Complex with N,N,S-Tridentate Ligand," Chem. J. Moldova. General, Industrial and Ecological Chemistry, vol. 2(1), pp. 102-107, 2007.

M. Mikuriya, T. Watanabe, A. Suyama, and D. Yoshioka, "Rhenium Complex with 2-[(2-Pyridylmethyl)amino]ethanethiol," X-ray Struct. Anal. Online, vol. 31, pp. 3-4, 2015. https://doi.org/10.2116/xraystruct.31.3

M. Mikuriya, K. Kusunoki, T. Kotera, D. Yoshioka, and K. Ogasawara, "Synthesis, Crystal Str ucture, and DFT Calculation of a Dioxido-bridged Dinuclear Oxidomolybdenum(V) Complex with 2-(2-Aminoethyl)aminoethanethiol," X-ray Struct. Anal. Online, vol. 33, pp. 37-39, 2017. https://doi.org/10.2116/xraystruct.33.37

M. Mikuriya, K. Kusunoki, T. Kotera, D. Yoshioka, S. Takemura, and K. Ogasawara, "Synthesis, Crystal Structure, and Relativistic DV-Xa Calculation of a µ-Oxido-µ-molybdato(VI)-bridged Dinuclear Oxidomolybdenum(V) Complex with 2-(3-Aminopropyl)aminoethanethiol," X-ray Struct. Anal. Online, vol. 34, pp. 19-21, 2018. https://doi.org/10.2116/xraystruct.34.19

T. Kotera, A. Fujita, M. Mikuriya, D. Yoshioka, T. Shibahara, K. Nishimoto, and M. Handa, “Cobalt Thiolates with Organic N,N,S-Tridentate Ligand: Conversion of Thiolate Complex to Sulfinate Complex via Sulfenate,” in IOP Conference Series: Materials Science and Engineering, vol. 835, p. 012024, 2020. https://doi.org/10.1088/1757-899X/835/1/012024

P. K. Mascharak, "Structural and functional models of nitrile hydratase," Coord. Chem. Rev., vol. 225, pp. 201-214, 2002. https://doi.org/10.1016/S0010-8545(01)00413-1

T. C. Harrop and P. K. Mascharak, "Fe(III) and Co(III) Centers with Carboxamide Nitrogen and Modified Sulfur Coordination: Lessons Learned from Nitrile Hydratase," Acc. Chem. Res., vol. 37, pp. 253-260, 2004. https://doi.org/10.1021/ar0301532

J. A. Kovacs, "Synthetic Analogues of Cysteinate-Ligated Non-Hem Iron and Non-Corrinoid Cobalt Enzymes," Chem. Rev., vol. 104, pp.825-848, 2004. https://doi.org/10.1021/cr020619e

W. Huang, J. Jia, J. Commings, M. Nelson, G. Schneider, and Y. Lindqvist, "Crystal structure of nitrile hydratase reveals a novel iron centre in a novel fold," Structure, vol. 5, pp. 691-699, 1997. https://doi.org/10.1016/S0969-2126(97)00223-2

S. Nagashima, M. Nakasato, N. Dohmae, M. Tsujimura, K. Takio, M. Okada, M. Yoshida, N. Kamiya, and I. Endo, "Novel non-heme iron center of nitrile hydratase with a claw setting of oxygen atoms," Nature Struct. Biol., vol. 5, pp. 347-351, 1998. https://doi.org/10.1038/nsb0598-347

O. Kahn, Molecular Magnetism, VCH Publications, New York, U.S.A. 1993, pp.3-4, ISBN 1-56081-566-3. https://doi.org/10.3390/magnetochemistry7030035

G. M. Sheldrick, "A short history of SHELX," Acta Crystallogr. Sect A, vol. 64, pp.112-122, 2008. https://doi.org/10.1134/S1087659616060092

K. Nakanishi, P. H. Solomon, and N. Furutachi, Infrared Absorption Spectroscopy (in Japanese), Nankodo, Tokyo, Japan, 1978.

K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, 6th ed., John Wiley & Sons, Hoboken, U.S.A., 2009, pp. 64-67, ISBN 978-0-471-74493-1. https://doi.org/10.1002/bbpc.19780821138

R. Grobelny, M. Melnik, and J. Mrozinski, Cobalt Coordination Compounds: Clasification and Analysis of Crystallographic and Structural Data, Dolnoslaskie Wydawnictwo Edukacyjne, Wroclaw, Poland, 1996.

Y. Murakami and K. Sakata, "Electronic Spectra of Metal Complexes," in Kireto Kagaku (in Japanese), K. Ueno, Ed., Nankodo, Tokyo, Japan, 1976, vol.1, pp. 91-396. (in Japanese)

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