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 PMe3 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 PMe3 ligands. The resulting desulfurized six-coordinate PCC iron complex also has an N2 ligand trans 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.