Oxygen Atom Transfer Catalysis with Homogenous and Polymer-Supported N,N- and N,N,O-Heteroscorpionate Dioxidomolybdenum(VI) Complexes

The N,N‐chelate ligand bis(3,5‐dimethyl‐4‐vinylpyrazol‐1‐yl)methane (bdmvpzm) and the N,N,O‐heteroscorpionate ligand bis(3,5‐dimethyl‐4‐vinylpyrazol‐1‐yl)acetic acid (Hbdmvpza), both with vinyl linkers suitable for copolymerisation, were synthesised under Vilsmeier–Haack conditions. The reactions of these ligands with [MoO2Cl2] yielded the corresponding molybdenum(VI) complexes [MoO2Cl2(bdmvpzm)] and [MoO2Cl(bdmvpza)], which were applied in oxygen atom transfer studies as mimics of dimethyl sulfoxide reductase (DMSO reductase). The catalytic properties of the homogeneous complexes and copolymers with embedded complexes were evaluated. The N,N‐chelate ligand bdmvpzm and the N,N,O‐heteroscorpionate ligand Hbdmvpza, both with vinyl linkers suitable for copolymerisation, are treated with [MoO2Cl2] to yield the molybdenum(VI) complexes [MoO2Cl2(bdmvpzm)] and [MoO2Cl(bdmvpza)]. The complexes and polymers with incorporated complexes are applied in oxygen‐transfer studies.