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The geometry of mononuclear copper(II) superoxide complexes has been shown to determine their ground state where side-on bonding leads to a singlet ground state and end-on complexes have triplet ground states. In an apparent contrast to this trend, the recently synthesized (HIPT3tren)Cu(II)O2(•-) (1) was proposed to have an end-on geometry and a singlet ground state. However, reexamination of 1 with resonance Raman, magnetic circular dichroism, and (2)H NMR spectroscopies indicate that 1 is, in fact, an end-on superoxide species with a triplet ground state that results from the single Cu(II)O2(•-) bonding interaction being weaker than the spin-pairing energy.

Correlation of the Electronic and Geometric Structures in Mononuclear Copper(II) Superoxide Complexes