Year: 2024
Type: article
Abstract: Electrophilic activation of the aromatic cyclo‐P5 ligand in [Cp*Fe(η5‐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(η5‐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(η4‐P5(1‐L)(2‐Me)][OTf] (L=IDipp (1), EtCAAC (2), IiPr (3 b)) and [Cp*Fe(η4‐P5(1‐IiPr)(1‐Me)][OTf] (3 a). For the first time, the much smaller IMe4 leads to the contraction of the cyclo‐P5 ligand and formation of [Cp*Fe(η4‐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(η4‐P5(1‐IDippCH2)(1/2‐Me)][OTf] (6 a/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{μ2,η4:3:1–P10Me2(IDippN)}][OTf] (8) and [{Cp*Fe}2{μ2,η4:1:1:1–P11Me2(IDipp)}][OTf] (9), respectively.
Source: Chemistry - A European Journal
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,640
Awards: G3204967036, G8018673321
OpenAlex ID: W4402990460