| Abstract: | A terminal Mo phosphide was prepared through the group transfer of both P and Cl atoms from chloro‐substituted dibenzo‐7λ3‐phosphanorbornadiene. This compound represents the first structurally characterized terminal transition‐metal phosphide with valence d electrons. In the tetragonal ligand field, these electrons populate an orbital of dxy parentage, an electronic configuration that accommodates both metal d electrons and a formal M≡P triple bond. Single‐electron oxidation affords a transient open‐shell terminal phosphide cation with significant spin density on P, as corroborated by continuous wave (CW) and pulse electron paramagnetic resonance (EPR) characterization. Facile P−P bond formation occurs from this species through intermolecular phosphide coupling. |
