Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Arsine, Stibine and Phosphine Derivatives of [Fe2(CO)6(μ-bdt)] (bdt = Benzenedithiolate) : Syntheses, Structures and Spectroscopic and Electrocatalytic Studies

Rahaman, Ahibur LU ; Kulsume, Ummey ; Alam, Fakir R. ; Haukka, Matti ; Ghosh, Shishir ; Hogarth, Graeme ; Nordlander, Ebbe LU and Kabir, Shariff E. (2025) In Inorganics 13(2).
Abstract

The reactivity of the benzenedithiolate (bdt)-bridged complex [Fe2(CO)6(µ-bdt)] with arsine, stibine and phosphine ligands has been studied. The new mono- and disubstituted complexes [Fe2(CO)5(EPh3)(µ-bdt)] (E = As, 1; E = Sb 3) and [Fe2(CO)4(EPh3)2(µ-bdt)] (E = As, 2; E = Sb, 4) and the previously reported [Fe2(CO)4(PPh2H)2(µ-bdt)] (5) have been prepared by Me3NO-initiated carbonyl substitution reactions of [Fe2(CO)6(µ-bdt)] with appropriate ligands at 80 °C. Spectroscopic and single-crystal X-ray diffraction studies reveal that in all cases the introduced... (More)

The reactivity of the benzenedithiolate (bdt)-bridged complex [Fe2(CO)6(µ-bdt)] with arsine, stibine and phosphine ligands has been studied. The new mono- and disubstituted complexes [Fe2(CO)5(EPh3)(µ-bdt)] (E = As, 1; E = Sb 3) and [Fe2(CO)4(EPh3)2(µ-bdt)] (E = As, 2; E = Sb, 4) and the previously reported [Fe2(CO)4(PPh2H)2(µ-bdt)] (5) have been prepared by Me3NO-initiated carbonyl substitution reactions of [Fe2(CO)6(µ-bdt)] with appropriate ligands at 80 °C. Spectroscopic and single-crystal X-ray diffraction studies reveal that in all cases the introduced ligands occupy apical coordination site(s) lying trans to the iron–iron bond. Their electrochemistry has been probed by cyclic voltammetry and selected complexes have been tested as proton reduction catalysts. Monosubstituted complexes 1 and 3 show two irreversible reductions at ca. −1.7 V and −2.0 V, respectively, relative to Fc+/Fc, while the disubstituted complexes 2 and 5 show a single irreversible reduction at ca. −2.2 V and −1.84 V, respectively. Complexes 1, 3 and 5 can catalyse electrocatalytic proton reduction in the presence of either p-toluene sulfonic acid (TsOH) or trifluoroacetic acid (CF3CO2H).

(Less)
Please use this url to cite or link to this publication:
author
; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
CO substitution, diiron-dithiolate complex, proton reduction, triphenylarsine, triphenylstibine
in
Inorganics
volume
13
issue
2
article number
63
publisher
MDPI AG
external identifiers
  • scopus:85218710748
ISSN
2304-6740
DOI
10.3390/inorganics13020063
language
English
LU publication?
yes
id
7eb416ac-f538-47a3-9610-1d794687d7bc
date added to LUP
2025-06-25 10:17:03
date last changed
2025-06-25 10:17:33
@article{7eb416ac-f538-47a3-9610-1d794687d7bc,
  abstract     = {{<p>The reactivity of the benzenedithiolate (bdt)-bridged complex [Fe<sub>2</sub>(CO)<sub>6</sub>(µ-bdt)] with arsine, stibine and phosphine ligands has been studied. The new mono- and disubstituted complexes [Fe<sub>2</sub>(CO)<sub>5</sub>(EPh<sub>3</sub>)(µ-bdt)] (E = As, 1; E = Sb 3) and [Fe<sub>2</sub>(CO)<sub>4</sub>(EPh<sub>3</sub>)<sub>2</sub>(µ-bdt)] (E = As, 2; E = Sb, 4) and the previously reported [Fe<sub>2</sub>(CO)<sub>4</sub>(PPh<sub>2</sub>H)<sub>2</sub>(µ-bdt)] (5) have been prepared by Me<sub>3</sub>NO-initiated carbonyl substitution reactions of [Fe<sub>2</sub>(CO)<sub>6</sub>(µ-bdt)] with appropriate ligands at 80 °C. Spectroscopic and single-crystal X-ray diffraction studies reveal that in all cases the introduced ligands occupy apical coordination site(s) lying trans to the iron–iron bond. Their electrochemistry has been probed by cyclic voltammetry and selected complexes have been tested as proton reduction catalysts. Monosubstituted complexes 1 and 3 show two irreversible reductions at ca. −1.7 V and −2.0 V, respectively, relative to Fc<sup>+</sup>/Fc, while the disubstituted complexes 2 and 5 show a single irreversible reduction at ca. −2.2 V and −1.84 V, respectively. Complexes 1, 3 and 5 can catalyse electrocatalytic proton reduction in the presence of either p-toluene sulfonic acid (TsOH) or trifluoroacetic acid (CF<sub>3</sub>CO<sub>2</sub>H).</p>}},
  author       = {{Rahaman, Ahibur and Kulsume, Ummey and Alam, Fakir R. and Haukka, Matti and Ghosh, Shishir and Hogarth, Graeme and Nordlander, Ebbe and Kabir, Shariff E.}},
  issn         = {{2304-6740}},
  keywords     = {{CO substitution; diiron-dithiolate complex; proton reduction; triphenylarsine; triphenylstibine}},
  language     = {{eng}},
  number       = {{2}},
  publisher    = {{MDPI AG}},
  series       = {{Inorganics}},
  title        = {{Arsine, Stibine and Phosphine Derivatives of [Fe<sub>2</sub>(CO)<sub>6</sub>(μ-bdt)] (bdt = Benzenedithiolate) : Syntheses, Structures and Spectroscopic and Electrocatalytic Studies}},
  url          = {{http://dx.doi.org/10.3390/inorganics13020063}},
  doi          = {{10.3390/inorganics13020063}},
  volume       = {{13}},
  year         = {{2025}},
}