Enhancing the Reactivity of an Aromatic cyclo‐P5 Ligand via Electrophilic Activation

Electrophilic activation of the aromatic cyclo‐P5 ligand in [Cp*Fe(h5‐P5)] is demonstrated to drastically enhance its reactivity towards weak nucleophiles. Unprecedented functionalized, contracted as well as complexly aggregated polyphosphorus compounds are accessed utilizing [Cp*Fe(h5‐P5Me)][OTf] (A), highlighting the great potential of this underexplored mode of reactivity. Addition of carbenes to A affords novel 1,2‐ or 1,1‐difunctionalized cyclo‐P5 complexes [Cp*Fe(h4‐P5(1‐L)(2‐Me)][OTf] (L = IDipp (1), EtCAAC (2), IiPr (3b)) and [Cp*Fe(h4‐P5(1‐IiPr)(1‐Me)][OTf] (3a). For the first time, the much smaller IMe4 leads to the contraction of the cyclo‐P5 ligand and formation of [Cp*Fe(h4‐P4(1‐IMe)(4‐Me)] (4). DFT calculations shed light on the delicate mechanism of this type of reaction, which is reinforced by the experimental identification of key intermediates. Even the comparably weak nucleophile IDippCH2 reacts with A to form [Cp*Fe(h4‐P5(1‐IDippCH2)(1/2‐Me)][OTf] (6a/b), highlighting its explicitly more reactive nature. Moreover, exposure of A to IDippEH (E = N, P) leads to a unique aggregation reaction affording [{Cp*Fe}2{m2,h4:3:1‑P10Me2(IDippN)}][OTf] (8) and [{Cp*Fe}2{m2,h4:1:1:1‑P11Me2(IDipp)}][OTf] (9), respectively.