Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals

We report on the structures of three unprecedented heteroleptic Sb-centered radicals [L(Cl)Ga](R)Sb^. (2-R, R=B[N(Dip)CH]₂ 2-B, 2,6-Mes₂ C₆ H₃ 2-C, N(SiMe₃ )Dip 2-N) stabilized by one electropositive metal fragment [L(Cl)Ga] (L=HC[C(Me)N(Dip)]₂ , Dip=2,6-i-Pr₂ C₆ H₃ ) and one bulky B- (2-B), C- (2-C), or N-based (2-N) substituent. Compounds 2-R are predominantly metal-centered radicals. Their electronic properties are largely influenced by the electronic nature of the ligands R, and significant delocalization of unpaired-spin density onto the ligands was observed in 2-B and 2-N. Cyclic voltammetry (CV) studies showed that 2-B undergoes a quasi-reversible one-electron reduction, which was confirmed by the synthesis of [K([2.2.2]crypt)][L(Cl)GaSbB[N(Dip)CH]₂ ] ([K([2.2.2]crypt)][2-B]) containing the stibanyl anion [2-B]^- , which was shown to possess significant Sb-B multiple-bonding character.