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Synthesis of phosphine derivatives of [Fe2(CO)6(μ-sdt)] (sdt = SCH2SCH2S) and investigation of their proton reduction capabilities

Hizbullah, Lintang LU ; Rahaman, Ahibur LU ; Safavi, Seyedeh ; Haukka, Matti ; Tocher, Derek A. ; Lisensky, George C. LU and Nordlander, Ebbe LU (2023) In Journal of Inorganic Biochemistry 246.
Abstract

The reactions of [Fe2(CO)6(μ-sdt)] (1) (sdt = SCH2SCH2S) with phosphine ligands have been investigated. Treatment of 1 with dppm (bis(diphenylphosphino)methane) or dcpm (bis(dicyclohexylphosphino)methane) affords the diphosphine-bridged products [Fe2(CO)4(μ-sdt)(μ-dppm)] (2) and [Fe2(CO)4(μ-sdt)(μ-dcpm)] (3), respectively. The complex [Fe2(CO)4(μ-sdt)(κ2-dppv)] (4) with a chelating diphosphine was obtained by reacting 1 with dppv (cis-1,2-bis(diphenylphosphino)ethene). Reaction of 1 with dppe (1,2-bis(diphenylphosphino)ethane) produces [{Fe2(CO)4(μ-sdt)}2(μ-κ1-dppe)] (5) in... (More)

The reactions of [Fe2(CO)6(μ-sdt)] (1) (sdt = SCH2SCH2S) with phosphine ligands have been investigated. Treatment of 1 with dppm (bis(diphenylphosphino)methane) or dcpm (bis(dicyclohexylphosphino)methane) affords the diphosphine-bridged products [Fe2(CO)4(μ-sdt)(μ-dppm)] (2) and [Fe2(CO)4(μ-sdt)(μ-dcpm)] (3), respectively. The complex [Fe2(CO)4(μ-sdt)(κ2-dppv)] (4) with a chelating diphosphine was obtained by reacting 1 with dppv (cis-1,2-bis(diphenylphosphino)ethene). Reaction of 1 with dppe (1,2-bis(diphenylphosphino)ethane) produces [{Fe2(CO)4(μ-sdt)}2(μ-κ1-dppe)] (5) in which the diphosphine forms an intermolecular bridge between two diiron cluster fragments. Three products were obtained when dppf (1,1′-bis(diphenylphosphino)ferrocene) was introduced to complex 1; they were [Fe2(CO)5(μ-sdt)(κ1-dppfO)] (6), the previously known [{Fe2(CO)5(μ-sdt)}2(μ-κ1-κ1-dppf)] (7), and [Fe2(CO)4(μ-sdt)(μ-dppf)] (8), with complex 8 being produced in highest yield. Single crystal X-ray diffraction analysis was performed on compounds 2, 3 and 8. All structures reveal the adoption of an anti-arrangement of the dithiolate bridges, while the diphosphines occupy dibasal positions. Infra-red spectroscopy indicates that the mono-substituted complexes 5, 6, and 7 are inert to protonation by HBF4.Et2O, but complexes 2, 3, 4 and [Fe2(CO)5(μ-sdt)(κ1-PPh3)] (9) show shifts of their ν(C-O) resonances that indicate that protons bind to the metal cores of the clusters. Addition of the one-electron oxidant [Cp2Fe]PF6 does not lead to any discernable shift in the IR resonances. The redox chemistry of the complexes was investigated by cyclic voltammetry, and the abilities of complexes to catalyze electrochemical proton reduction were examined.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Cyclic voltammetry, Electrocatalysis, Hydrogenase, Iron carbonyl complex, Phosphine, Proton reduction
in
Journal of Inorganic Biochemistry
volume
246
article number
112272
publisher
Elsevier
external identifiers
  • pmid:37339572
  • scopus:85162091640
ISSN
0162-0134
DOI
10.1016/j.jinorgbio.2023.112272
language
English
LU publication?
yes
id
13ded3e3-4374-4391-b704-c1a62cecebf1
date added to LUP
2023-09-01 15:29:27
date last changed
2024-04-20 02:24:57
@article{13ded3e3-4374-4391-b704-c1a62cecebf1,
  abstract     = {{<p>The reactions of [Fe<sub>2</sub>(CO)<sub>6</sub>(μ-sdt)] (1) (sdt = SCH<sub>2</sub>SCH<sub>2</sub>S) with phosphine ligands have been investigated. Treatment of 1 with dppm (bis(diphenylphosphino)methane) or dcpm (bis(dicyclohexylphosphino)methane) affords the diphosphine-bridged products [Fe<sub>2</sub>(CO)<sub>4</sub>(μ-sdt)(μ-dppm)] (2) and [Fe<sub>2</sub>(CO)<sub>4</sub>(μ-sdt)(μ-dcpm)] (3), respectively. The complex [Fe<sub>2</sub>(CO)<sub>4</sub>(μ-sdt)(κ<sup>2</sup>-dppv)] (4) with a chelating diphosphine was obtained by reacting 1 with dppv (cis-1,2-bis(diphenylphosphino)ethene). Reaction of 1 with dppe (1,2-bis(diphenylphosphino)ethane) produces [{Fe<sub>2</sub>(CO)<sub>4</sub>(μ-sdt)}<sub>2</sub>(μ-κ<sup>1</sup>-dppe)] (5) in which the diphosphine forms an intermolecular bridge between two diiron cluster fragments. Three products were obtained when dppf (1,1′-bis(diphenylphosphino)ferrocene) was introduced to complex 1; they were [Fe<sub>2</sub>(CO)<sub>5</sub>(μ-sdt)(κ<sup>1</sup>-dppfO)] (6), the previously known [{Fe<sub>2</sub>(CO)<sub>5</sub>(μ-sdt)}<sub>2</sub>(μ-κ<sup>1</sup>-κ<sup>1</sup>-dppf)] (7), and [Fe<sub>2</sub>(CO)<sub>4</sub>(μ-sdt)(μ-dppf)] (8), with complex 8 being produced in highest yield. Single crystal X-ray diffraction analysis was performed on compounds 2, 3 and 8. All structures reveal the adoption of an anti-arrangement of the dithiolate bridges, while the diphosphines occupy dibasal positions. Infra-red spectroscopy indicates that the mono-substituted complexes 5, 6, and 7 are inert to protonation by HBF<sub>4</sub>.Et<sub>2</sub>O, but complexes 2, 3, 4 and [Fe<sub>2</sub>(CO)<sub>5</sub>(μ-sdt)(κ<sup>1</sup>-PPh<sub>3</sub>)] (9) show shifts of their ν<sub>(C-O)</sub> resonances that indicate that protons bind to the metal cores of the clusters. Addition of the one-electron oxidant [Cp<sub>2</sub>Fe]PF<sub>6</sub> does not lead to any discernable shift in the IR resonances. The redox chemistry of the complexes was investigated by cyclic voltammetry, and the abilities of complexes to catalyze electrochemical proton reduction were examined.</p>}},
  author       = {{Hizbullah, Lintang and Rahaman, Ahibur and Safavi, Seyedeh and Haukka, Matti and Tocher, Derek A. and Lisensky, George C. and Nordlander, Ebbe}},
  issn         = {{0162-0134}},
  keywords     = {{Cyclic voltammetry; Electrocatalysis; Hydrogenase; Iron carbonyl complex; Phosphine; Proton reduction}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Journal of Inorganic Biochemistry}},
  title        = {{Synthesis of phosphine derivatives of [Fe<sub>2</sub>(CO)<sub>6</sub>(μ-sdt)] (sdt = SCH<sub>2</sub>SCH<sub>2</sub>S) and investigation of their proton reduction capabilities}},
  url          = {{http://dx.doi.org/10.1016/j.jinorgbio.2023.112272}},
  doi          = {{10.1016/j.jinorgbio.2023.112272}},
  volume       = {{246}},
  year         = {{2023}},
}