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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 (2021) KEMR32 20201
Department of Chemistry
Abstract
The reactions of [Fe2(CO)6(µ-sdt)] (1) (sdt = SCH2SCH2S) with diphosphine ligands have been investigated. New diiron complexes that can serve as model complexes for the active sites of [FeFe]-hydrogenases were obtained from these reactions. Treatment of 1 with the dppm (bis(diphenylphosphino)methane) and the dcpm (bis(dicyclohexylphosphino)methane) ligands 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... (More)
The reactions of [Fe2(CO)6(µ-sdt)] (1) (sdt = SCH2SCH2S) with diphosphine ligands have been investigated. New diiron complexes that can serve as model complexes for the active sites of [FeFe]-hydrogenases were obtained from these reactions. Treatment of 1 with the dppm (bis(diphenylphosphino)methane) and the dcpm (bis(dicyclohexylphosphino)methane) ligands 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(diphenylphosphine)ferrocenyl) was introduced to complex 1; they were [Fe2(CO)4(µ-sdt)( κ1-dppfO)] (6), [{Fe2(CO)4(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 and 4 show shifts of their (C-O) resonances that indicate that protons bind to the metal 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 the complexes to catalyze electrochemical proton reduction were examined. (Less)
Popular Abstract
Forecast on the energy consumption indicates a surge demand globally within next decade. Concurrently, fossil fuel plays pivotal role as energy source and industry component which contributes to our present problems. Several alternatives have been investigated, one of the promising candidates is hydrogen. It has energy output as much as oil produce, emit water as byproduct, and sustainably abundance in a form of gas and water. Hydrogen also industrially applicable as raw material for producing fertilizer, refining petroleum process, metal purification by reduction, etc. The invented process that effectively produce hydrogen is by using platinum catalyst which is a noble metal. Thus, an endeavor to hydrogen economy is a fascinating goal. On... (More)
Forecast on the energy consumption indicates a surge demand globally within next decade. Concurrently, fossil fuel plays pivotal role as energy source and industry component which contributes to our present problems. Several alternatives have been investigated, one of the promising candidates is hydrogen. It has energy output as much as oil produce, emit water as byproduct, and sustainably abundance in a form of gas and water. Hydrogen also industrially applicable as raw material for producing fertilizer, refining petroleum process, metal purification by reduction, etc. The invented process that effectively produce hydrogen is by using platinum catalyst which is a noble metal. Thus, an endeavor to hydrogen economy is a fascinating goal. On the other hand, nature has been harvesting hydrogen using active enzyme for millennia, on one of which consist of [FeFe]-hydrogenase cluster in its active site. Iron as the metal core of the component is far more abundant than platinum emphasizing the scale up of the facility is possible industrially. In this study, several novel diiron carbonyl clusters have been synthesized to bio mimic such a structure and revealed the potential in hydrogen production electrochemically. Structure characterization is proven by IR and NMR spectroscopy, and its electrochemical properties are identified by cyclic voltammetry. The complexes exhibit proton reduction activity, via electron donation from metal to the proton that attracted to the metal followed by another reduction to the second proton. (Less)
Please use this url to cite or link to this publication:
author
Hizbullah, Lintang LU
supervisor
organization
course
KEMR32 20201
year
type
H2 - Master's Degree (Two Years)
subject
keywords
Diiron hydrogenase, diphosphines derivatives, proton reduction, electrocatalytic, inorganic chemistry
language
English
id
9044494
date added to LUP
2021-05-21 09:07:50
date last changed
2021-05-21 12:18:54
@misc{9044494,
  abstract     = {{The reactions of [Fe2(CO)6(µ-sdt)] (1) (sdt = SCH2SCH2S) with diphosphine ligands have been investigated. New diiron complexes that can serve as model complexes for the active sites of [FeFe]-hydrogenases were obtained from these reactions. Treatment of 1 with the dppm (bis(diphenylphosphino)methane) and the dcpm (bis(dicyclohexylphosphino)methane) ligands 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(diphenylphosphine)ferrocenyl) was introduced to complex 1; they were [Fe2(CO)4(µ-sdt)( κ1-dppfO)] (6), [{Fe2(CO)4(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 and 4 show shifts of their (C-O) resonances that indicate that protons bind to the metal 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 the complexes to catalyze electrochemical proton reduction were examined.}},
  author       = {{Hizbullah, Lintang}},
  language     = {{eng}},
  note         = {{Student Paper}},
  title        = {{Synthesis of Phosphine Derivatives of [Fe2(CO)6(µ-sdt)] (sdt = SCH2SCH2S) and Investigation of Their Proton Reduction Capabilities}},
  year         = {{2021}},
}