Electron-Transfer Chain Catalysis of η2‑Arene, η2‑Alkene, and η2‑Ketone Exchange on Molybdenum
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An oxidant-initiated, substitution process for dihapto-coordinated ligands is described for the {MoTp(NO)(DMAP)} system. Complexes of the form MoTp(NO)(DMAP)(η2-alkene), MoTp(NO)(DMAP)(η2-ketone), and MoTp(NO)(DMAP)(η2-arene) (where Tp = hydridotris(pyrazolyl)borate and DMAP = 4-(dimethylamino)pyridine) undergo an alkene-to-ketone exchange that is catalyzed by the addition of 2) and monocoordinated (κ-O) isomers and the differing redox characteristics of these two isomeric forms. This concept was then applied to the search of sodium-free reduction conditions for the conversion of MoTp(NO)(DMAP)(I) to various molybdenum(0) complexes of unsaturated ligands, including MoTp(NO)(DMAP)(η2-naphthalene) and MoTp(NO)(DMAP)(α-pinene).
