Organometallic copper complexes are widely used in organic synthesis and transition-metal-mediated catalysis. However, the chemistry of isolable organocopper complexes has generally been limited to anionic organocuprates or neutral species and dominated by the copper(I) oxidation state, with careful studies often hampered by aggregation. An unexpectedly electrophilic dicopper complex supported by a rigid, naphthyridine-based ligand enabled the synthesis of persistent, discrete, and cationic dicopper complexes with a range of symmetrically bridging hydrocarbyl moieties. Electrochemical characterization of these species led to the synthesis and isolation of rare mixed-valence organocopper complexes. Electronic and variable-temperature electron paramagnetic resonance spectroscopy revealed varying degrees of spin localization, consistent with a loss in symmetry between the two copper centers. In addition, reactivity studies have investigated the role these organometallic dicopper(I,I) and dicopper(I,II) complexes could have in catalysis.

Organometallic cationic dicopper complexes: Synthesis, mixed-valence, reactivity, and their role in catalysis

253rd National Meeting (2017)

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