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

Helling, Christoph; Cutsail III, George E.; Weinert, Hanns; Woelper, Christoph; Schulz, Stephan

doi:10.1002/anie.202000586

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

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Cutsail III, George E.
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Helling, C., Cutsail III, G. E., Weinert, H., Woelper, C., & Schulz, S. (2020). Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals. ANGEWANDTE CHEMIE INTERNATIONAL EDITION, 59(19), 7561-7568. doi:10.1002/anie.202000586.

Cite as: https://hdl.handle.net/21.11116/0000-0007-B321-9

Abstract

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-Mes(2)C(6)H(3) 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-Pr2C6H3) 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.