For a long time, Co(CO)4 has been proposed to be a crucial active intermediate in industrial hydroformylation and carbonylation. However, the mechanism of the processes has never been fully proved due to the high reactivity and unstability of Co(CO)4. A zerovalent radical Co(CNArMes2)4 was successfully isolated by utilize of a sterically encumbering m-terphenyl isocyanide (CNArMes2) (Mes = 2,4,6-Me3C6H2) acting as an isolobal analogue of CO. Herein, we show that Co(CNArMes2)4 can undergo ligand exchange reactions with phosphines, alkynes and alkenes to generate the corresponding CoL(CNArMes2)3. More interestingly, It also reacts with stable radical like TEMPO (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl), forming a diamagnetic η2-TEMPOCo(CNArMes2)2. Our finding may provide hints to understand the key role of Co(CO)4.

Co(CNArMes2)4, an isolobal analogue of Co(CO)4, and its reactivity

251st National Meeting (2016)

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