AI Article Synopsis
- Metal insertion into C-S bonds of thiophenes creates new ligand designs with carbon (C) and sulfur (S) donors.
- The study focuses on iron-mediated C-S activation using a diphenylphosphine-functionalized benzothiophene proligand, resulting in a five-coordinate, diamagnetic iron(II) complex.
- The complex undergoes reduction leading to significant structural changes, including bond cleavage and ligand transformation, ultimately allowing for the formation of novel pincers containing thiolates and phosphides that are hard to achieve via traditional methods.
Article Abstract
Metal insertion into the C-S bonds of thiophenes is a facile route to interesting polydentate ligand scaffolds with C and S donors. Here, we describe iron-mediated C-S activation of a diphenylphosphine-functionalized benzothiophene proligand. Metalation of the proligand with "tetrakis(trimethylphosphine)iron" gives an initial five-coordinate, diamagnetic iron(II) species with two PMe ligands and a dianionic PCS pincer ligand. Upon one-electron reduction, a reactive anionic iron(I) complex is formed. This species then undergoes deep-seated changes, notably cleavage of C-S and C-P bonds in the supporting ligand. Substantial coordination sphere alterations accompany the ligand C-S bond activation, including loss of a sulfur anion from the S-Fe-C metallacycle and reorganization of the two PMe ligands. The resulting desulfurized six-coordinate PCC iron complex also has an N ligand to the vinyl C. Reducing this complex then cleaves a C-P bond in the appended diphenylphosphine, giving a phosphido arm. These ligand transformations demonstrate novel approaches to pincers with thiolates and phosphides, which would be difficult to synthesize using typical methods through free ligand salts.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10810089 | PMC |
| http://dx.doi.org/10.1021/acs.organomet.3c00220 | DOI Listing |
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