Titanium Complexes with Functional Alkoxido Ligands for Selective Ethylene Dimerization – A High Throughput Experimentation Approach

New titanium complexes of general formula [Ti(OR)2(OiPr)2], containing functionalized alkoxido ligands, were developed for the selective catalytic dimerization of ethylene to 1‐butene using a combined High Throughput Screening (HTS) / Design of Experiment (DoE) approach. First, a library of 19 ligands was elaborated and a primary screening spotted the phosphorus‐functionalized alkoxido ligands as most promising. A second, more focused library containing 8 alkoxidophosphane ligands was then developed. A longer linear spacer between the alkoxido and the phosphorus functions, as in [Ti(19)2(OiPr)2], was found beneficial for this catalytic reaction. After identification of the best co‐catalyst (AlEt3) and co‐ligand (OnBu), final optimization of the reaction conditions was performed using a design of experiments (DoE) approach. The complex [Ti(19)2(OnBu)2] was shown to selectively dimerize ethylene in 1‐butene (C4(α)=93 % (99+%)) at 30 bar C2H4 and 55 °C with AlEt3 as co‐catalyst, resulting in very high activity and selectivity for a molecular titanium catalyst (13000 g gTi−1 h−1, 93 % 1‐butene). Winning Ti! A combined High Throughput Screening (HTS) / Design of Experiment (DoE) approach, applied to functionalized alkoxido titanium complexes [Ti(OR)2(OiPr)2], allowed to identify a very active and selective Ti‐based catalyst for ethylene dimerization (13000 g gTi−1 h−1, 93 % 1‐butene) (30 bar C2H4, 55 °C, co‐catalyst AlEt3).