Preparation and characterization of homologous diiron dithiolato, diselenato, and ditellurato complexes: [FeFe]-hydrogenase models

Mohammad K. Harb, Ulf Peter Apfel, Joachim Kübel, Helmar Görls, Greg A N Feiton, Taka Sakamoto, Dennis H. Evans, Richard S Glass, Dennis L Lichtenberger, Mohammad El-khateeb, Wolfgang Weigand

Research output: Contribution to journalArticle

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Abstract

In order to elucidate the influence of the bridging chalcogen atoms in hydrogenase model complexes, diiron dithiolato, diselenolato, and ditellurolato complexes have been prepared and characterized. Treatment of Fe 3(CO)12 with 3,3-bis(thiocyanatomethyl)oxetane (1) or a mixture of 2-oxa-6,7-dithiaspiro[3.4]octane (2a) and 2-oxa-6,7,8-trithiaspiro[3. 5]nonane (2b) in toluene at reflux afforded the model compound Fe 2(μ-S2C5H8O)(CO)6 (3). The analogous diselenolato and ditellurolato complexes, Fe2(μ- Se2C5H8O)(CO)6 (4) and Fe 2(μ-Te2C5H8O)(CO)6 (5), were obtained from the reaction of Fe3(CO)12 with 2-oxa-6,7-diselenaspiro[3.4]octane (6) and 2-oxa-6,7-ditelluraspiro[3.4]octane (7), respectively. Compounds 3-5 were characterized by spectroscopic techniques (NMR, IR, photoelectron spectroscopy), mass spectrometry, single-crystal X-ray analysis, and computational modeling. The electrochemical properties for the new compounds have been studied to assess their ability to catalyze electrochemical reduction of protons to give dihydrogen, and the catalytic rate is found to decrease on going from the sulfur to selenium to tellurium compounds. In the series 3-5 the reorganization energy on going to the corresponding cation decreased from 3 to 4 to 5. Spectroscopic and computational analysis suggests that the increasing size of the chalcogen atoms from S to Se to Te increases the Fe-Fe distance and decreases the ability of the complex to form the structure with a rotated Fe(CO)3 group that has a bridging carbonyl ligand and a vacant coordination site for protonation. This effect is mirrored on reduction of 3-5 in that the rotated structure with a bridging carbonyl, which creates a vacant coordination site for protonation, is disfavored on going from the S to Se to Te complexes.

Original languageEnglish (US)
Pages (from-to)6666-6675
Number of pages10
JournalOrganometallics
Volume28
Issue number23
DOIs
StatePublished - Dec 14 2009

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Hydrogenase
octanes
Carbon Monoxide
Chalcogens
preparation
tellurium compounds
Protonation
nonanes
spectroscopic analysis
Tellurium compounds
selenium
atoms
toluene
sulfur
mass spectroscopy
Atoms
photoelectron spectroscopy
X ray analysis
Toluene
cations

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Harb, M. K., Apfel, U. P., Kübel, J., Görls, H., Feiton, G. A. N., Sakamoto, T., ... Weigand, W. (2009). Preparation and characterization of homologous diiron dithiolato, diselenato, and ditellurato complexes: [FeFe]-hydrogenase models. Organometallics, 28(23), 6666-6675. https://doi.org/10.1021/om900675q

Preparation and characterization of homologous diiron dithiolato, diselenato, and ditellurato complexes : [FeFe]-hydrogenase models. / Harb, Mohammad K.; Apfel, Ulf Peter; Kübel, Joachim; Görls, Helmar; Feiton, Greg A N; Sakamoto, Taka; Evans, Dennis H.; Glass, Richard S; Lichtenberger, Dennis L; El-khateeb, Mohammad; Weigand, Wolfgang.

In: Organometallics, Vol. 28, No. 23, 14.12.2009, p. 6666-6675.

Research output: Contribution to journalArticle

Harb, MK, Apfel, UP, Kübel, J, Görls, H, Feiton, GAN, Sakamoto, T, Evans, DH, Glass, RS, Lichtenberger, DL, El-khateeb, M & Weigand, W 2009, 'Preparation and characterization of homologous diiron dithiolato, diselenato, and ditellurato complexes: [FeFe]-hydrogenase models', Organometallics, vol. 28, no. 23, pp. 6666-6675. https://doi.org/10.1021/om900675q
Harb, Mohammad K. ; Apfel, Ulf Peter ; Kübel, Joachim ; Görls, Helmar ; Feiton, Greg A N ; Sakamoto, Taka ; Evans, Dennis H. ; Glass, Richard S ; Lichtenberger, Dennis L ; El-khateeb, Mohammad ; Weigand, Wolfgang. / Preparation and characterization of homologous diiron dithiolato, diselenato, and ditellurato complexes : [FeFe]-hydrogenase models. In: Organometallics. 2009 ; Vol. 28, No. 23. pp. 6666-6675.
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N2 - In order to elucidate the influence of the bridging chalcogen atoms in hydrogenase model complexes, diiron dithiolato, diselenolato, and ditellurolato complexes have been prepared and characterized. Treatment of Fe 3(CO)12 with 3,3-bis(thiocyanatomethyl)oxetane (1) or a mixture of 2-oxa-6,7-dithiaspiro[3.4]octane (2a) and 2-oxa-6,7,8-trithiaspiro[3. 5]nonane (2b) in toluene at reflux afforded the model compound Fe 2(μ-S2C5H8O)(CO)6 (3). The analogous diselenolato and ditellurolato complexes, Fe2(μ- Se2C5H8O)(CO)6 (4) and Fe 2(μ-Te2C5H8O)(CO)6 (5), were obtained from the reaction of Fe3(CO)12 with 2-oxa-6,7-diselenaspiro[3.4]octane (6) and 2-oxa-6,7-ditelluraspiro[3.4]octane (7), respectively. Compounds 3-5 were characterized by spectroscopic techniques (NMR, IR, photoelectron spectroscopy), mass spectrometry, single-crystal X-ray analysis, and computational modeling. The electrochemical properties for the new compounds have been studied to assess their ability to catalyze electrochemical reduction of protons to give dihydrogen, and the catalytic rate is found to decrease on going from the sulfur to selenium to tellurium compounds. In the series 3-5 the reorganization energy on going to the corresponding cation decreased from 3 to 4 to 5. Spectroscopic and computational analysis suggests that the increasing size of the chalcogen atoms from S to Se to Te increases the Fe-Fe distance and decreases the ability of the complex to form the structure with a rotated Fe(CO)3 group that has a bridging carbonyl ligand and a vacant coordination site for protonation. This effect is mirrored on reduction of 3-5 in that the rotated structure with a bridging carbonyl, which creates a vacant coordination site for protonation, is disfavored on going from the S to Se to Te complexes.

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