A Highly Reduced V<sub>2</sub><sup>3+</sup> Unit with a Metal−Metal Bond Order of 3.5

We report the isolation and structural characterization of the first four-bladed paddlewheel complex having an M<sub>2</sub><sup>3+</sup> core in K(THF)<sub>3</sub>[V<sub>2</sub>(DPhF)<sub>4</sub>], where DPhF is the anion of <i>N</i>,<i>N</i>‘-diphenylformamidine. This dark green, paramagnetic compound was obtained by reduction of diamagnetic, triply bonded V<sub>2</sub>(DPhF)<sub>4</sub> with KC<sub>8</sub>. The V−V bond distance in K(THF)<sub>3</sub>[V<sub>2</sub>(DPhF)<sub>4</sub>] is 1.9295(8) Å, 0.05 Å shorter than that found in the V<sub>2</sub><sup>4+</sup> species. The shortening of the bond, combined with a 15-line hyperfine splitting pattern in the EPR spectrum of K(THF)<sub>3</sub>[V<sub>2</sub>(DPhF)<sub>4</sub>], indicates that the unpaired electron is delocalized over the two vanadium atoms, giving rise to a bond order of 3.5.