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
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...
Saved in:
| Main Authors: | , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-02-01
|
| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/13/2/63 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | 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, <b>1</b>; E = Sb <b>3</b>) and [Fe<sub>2</sub>(CO)<sub>4</sub>(EPh<sub>3</sub>)<sub>2</sub>(µ-bdt)] (E = As, <b>2</b>; E = Sb, <b>4</b>) and the previously reported [Fe<sub>2</sub>(CO)<sub>4</sub>(PPh<sub>2</sub>H)<sub>2</sub>(µ-bdt)] (<b>5</b>) 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 <i>trans</i> 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 <b>1</b> and <b>3</b> show two irreversible reductions at <i>ca.</i> −1.7 V and −2.0 V, respectively, relative to Fc<sup>+</sup>/Fc, while the disubstituted complexes <b>2</b> and <b>5</b> show a single irreversible reduction at <i>ca</i>. −2.2 V and −1.84 V, respectively. Complexes <b>1</b>, <b>3</b> and <b>5</b> can catalyse electrocatalytic proton reduction in the presence of either <i>p</i>-toluene sulfonic acid (TsOH) or trifluoroacetic acid (CF<sub>3</sub>CO<sub>2</sub>H). |
|---|---|
| ISSN: | 2304-6740 |