The synthesis and reactivity of the first series of monoanionic bidentate ligands containing an N-heterocyclic carbene−phosphinidene adduct and their corresponding half-metallocene titanium complexes were investigated. The structural characterization of 5a confirmed bidentate coordination through the phosphorus and oxygen atoms of the ligand, with evidence of significant electron delocalization over the ligand structure. The new titanium complexes produced polyethylene at room temperature and under 1 atm of ethylene at a rate of up to 9.2 kg PE mol Ti −1 h −1 .
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