Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease

Way Zen Lee, Huan Sheng Tseng, Tzu Li Wang, Hui Lien Tsai, Ting Shen Kuo

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

A disubstituted benzoate polydentate ligand, 2,6-bis[bis(pyridinyl-2- methyl)aminoethoxyl]benzoate (HL), was prepared to synthesize nickel mimics for the active site of urease. Reaction of the deprotonated L- with Ni(ClO4)2 · 6H2O afforded a dinickel complex, [LNi2(CH3CN)(THF)](ClO4)3 (1), characterized by UV/vis spectroscopy and X-ray crystallography. Addition of urea to an acetonitrile solution of 1 afforded a dinickel urea adduct, [LNi2(urea)2](ClO4)3 · 2CH3CN (2), which was structurally and spectroscopically characterized. 1H NMR and ESI-MS spectra of 2 both evidenced that urea molecules remained coordinated to the nickel centers of 2 in solution. With the inspiration of urea coordination to the nickel centers of 1, the conjugate additions of thiophenols to α,β-enones catalyzed by complex 1 were examined and found to proceed in good yields. In contrast, the same catalytic reaction by Ni(ClO4)2 · 6H2O and HL was far less effective. Also, addition of NaOAc or NaOAcPh2 to an acetonitrile solution of 1 gave tetranuclear nickel complexes, [LNi 2-(μ-OAc)]2(ClO4)4 · 3H2O (3) and [LNi2(μ-OAcPh2)] 2(ClO4)4 · 5CH3CN · 2THF (4), and their molecular structures determined by X-ray diffraction can be described as dimers of dimers. Each dinickel core of 3 and 4 closely mimics the active site of urease. The magnetic data of 1, 3, and 4 exhibited a very weak antiferromagnetic coupling (J =-0.72 cm-1 for 1,-0.65 cm-1 for 3 and 4) between two metal centers in the dinickel core.

Original languageEnglish
Pages (from-to)2874-2881
Number of pages8
JournalOrganometallics
Volume29
Issue number13
DOIs
Publication statusPublished - 2010 Jul 12

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Urease
Benzoates
Nickel
ureas
Urea
nickel
acetonitrile
Dimers
dimers
inspiration
X ray crystallography
adducts
crystallography
Ultraviolet spectroscopy
x rays
molecular structure
Molecular structure
perchlorate
thiophenol
Metals

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease. / Lee, Way Zen; Tseng, Huan Sheng; Wang, Tzu Li; Tsai, Hui Lien; Kuo, Ting Shen.

In: Organometallics, Vol. 29, No. 13, 12.07.2010, p. 2874-2881.

Research output: Contribution to journalArticle

Lee, Way Zen ; Tseng, Huan Sheng ; Wang, Tzu Li ; Tsai, Hui Lien ; Kuo, Ting Shen. / Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease. In: Organometallics. 2010 ; Vol. 29, No. 13. pp. 2874-2881.
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abstract = "A disubstituted benzoate polydentate ligand, 2,6-bis[bis(pyridinyl-2- methyl)aminoethoxyl]benzoate (HL), was prepared to synthesize nickel mimics for the active site of urease. Reaction of the deprotonated L- with Ni(ClO4)2 · 6H2O afforded a dinickel complex, [LNi2(CH3CN)(THF)](ClO4)3 (1), characterized by UV/vis spectroscopy and X-ray crystallography. Addition of urea to an acetonitrile solution of 1 afforded a dinickel urea adduct, [LNi2(urea)2](ClO4)3 · 2CH3CN (2), which was structurally and spectroscopically characterized. 1H NMR and ESI-MS spectra of 2 both evidenced that urea molecules remained coordinated to the nickel centers of 2 in solution. With the inspiration of urea coordination to the nickel centers of 1, the conjugate additions of thiophenols to α,β-enones catalyzed by complex 1 were examined and found to proceed in good yields. In contrast, the same catalytic reaction by Ni(ClO4)2 · 6H2O and HL was far less effective. Also, addition of NaOAc or NaOAcPh2 to an acetonitrile solution of 1 gave tetranuclear nickel complexes, [LNi 2-(μ-OAc)]2(ClO4)4 · 3H2O (3) and [LNi2(μ-OAcPh2)] 2(ClO4)4 · 5CH3CN · 2THF (4), and their molecular structures determined by X-ray diffraction can be described as dimers of dimers. Each dinickel core of 3 and 4 closely mimics the active site of urease. The magnetic data of 1, 3, and 4 exhibited a very weak antiferromagnetic coupling (J =-0.72 cm-1 for 1,-0.65 cm-1 for 3 and 4) between two metal centers in the dinickel core.",
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