Resurgence of Organomanganese(I) Chemistry. Bidentate Manganese(I) Phosphine–Phenol(ate) Complexes

As part of the United Nations 2019 celebration of the periodic table of elements, we are privileged to present our studies with the element manganese in this Forum Article series. Catalysis with organomanganese­(I) complexes has recently emerged as an important area with the discovery that pincer manganese­(I) complexes that can activate substrates through metal–ligand cooperative mechanisms are active (de)­hydrogenation catalysts. However, this rapidly growing field faces several challenges, and we identify these in this Forum Article. Some of our efforts in addressing these challenges include using alternative precursors to Mn­(CO)5Br to prepare manganese­(I) dicarbonyl complexes, the latter of which is usually a component of active catalysts. Specifically, the synthesis of a new bidentate phosphine–phenol ligand along with its corresponding coordination chemistry of five new manganese­(I) complexes is described. The complexes having two phenol–phenolate moieties interact with the secondary coordination sphere to enable facile loss of the bromido ligand and even one of the CO ligands to afford manganese­(I) dicarbonyl centers.