Robust Chromium Precursors for Catalysis: Isolation and Structure of a Single-Component Ethylene Tetramerization Precatalyst

We have introduced a new class of stable organometallic Cr reagents (compounds 1-4) that are readily prepared, yet reactive enough to serve as precursors. They were used for ethylene tetramerization catalysis following stoichiometric activation by in situ protonation. This study highlights the importance of balancing stability with reactivity in generating an organometallic precursor that is useful in catalysis. Moreover, precursor 4 allowed for the isolation and crystallographic characterization of a room-temperature stable cationic species, (PNP)CrR₂⁺ (R = o-C₆H₄(CH₂)₂OMe, PNP = ⁱPrN(PPh₂)₂). This complex (5) may be used as a single component precatalyst, without any alkylaluminum reagents. This result provides an unprecedented level of insight into the kind of structures that must be produced from more complicated activation processes.