Bis(neopentylglycolato)diboron (b2nep2) As a Bidentate Ligand and a Reducing Agent for Early Transition Metal Chlorides Giving MCl4(B2nep2) Complexes.

We found that bis(neopentylglycolato)diboron (B2nep2) served as a bidentate ligand and a one-electron reducing agent for early transition metal chlorides to afford MCl4(B2nep2). Treatment of B2nep2 with MCl5 (M = Nb and Mo) produced MCl4(B2nep2) via two successive reactions, coordination of B2nep2 to the metal center and one-electron reduction from M(V) to M(IV), while coordination of B2nep2 to MCl4 (M = Zr, Ti) was observed without reduction of the central metals. DFT studies for the reduction of NbCl5 by B2nep2 clarified the initial formation of seven-coordinated and B2nep2-ligated Nb(V) species, NbCl5(B2nep2), and one chloride on niobium(V) moves to the Lewis acidic boron center to generate NbCl4[(B2nep2)Cl]. The chloride on the boron atom of NbCl4[(B2nep2)Cl] is trapped by the second B2nep2 to give [NbCl4(B2nep2)][ClB2nep2]. After the formation of [ClB2nep2]- as an anionic sp2-sp3 diboron adduct, one-electron reduction of the niobium(V) center produces NbCl4(B2nep2) along with [ClB2nep2]˙ as a plausible diboron species, whose decomposition affords ClBnep and B2nep2. The reduction of metal halides in the presence of B2nep2 was exemplified by green LED irradiation of TiCl4(B2nep2), producing chloride-bridged titanium(III) species, (B2nep2)TiCl2(μ-Cl)2TiCl2(B2nep2).