Isolable
Diphosphorus-Centered Radical Anion and Diradical
Dianion
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Abstract
Two salts containing
diphosphorus-centered radical anion <b>1</b><sup>•–</sup> and diradical dianion <b>1</b><sup>2–••</sup> were obtained by one- and two-electron
reductions of an indenofluorene-bridging diphosphaalkene (<b>1</b>) with K and KC<sub>8</sub>, respectively. The salts have been characterized
by electron paramagnetic resonance (EPR) spectroscopy, UV–vis
absorption spectroscopy, and single-crystal X-ray diffraction analysis.
EPR spectroscopy and theoretical calculations reveal that the spin
density of the radicals mainly resides on the phosphorus atoms, and <b>1</b><sup>2–••</sup> has an open-shell singlet
ground state. <b>1</b><sup>•–</sup> and <b>1</b><sup>2–••</sup> represent the first
isolable and structurally characterized diphosphorus-centered radical
anion and dianion