Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals |
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| Authors: | M?Sc Christoph Helling Dr George E Cutsail III M?Sc Hanns Weinert Dr Christoph Wölper Prof?Dr Stephan Schulz |
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| Institution: | 1. Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide), University of Duisburg-Essen, Universitätsstraße 5–7, 45117 Essen, Germany;2. Max Planck Institute for Chemical Energy Conversion (CEC), Stiftstraße 34–36, 45470 Mülheim an der Ruhr, Germany |
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| Abstract: | We report on the structures of three unprecedented heteroleptic Sb-centered radicals L(Cl)Ga](R)Sb. ( 2-R , R=BN(Dip)CH]2 2-B , 2,6-Mes2C6H3 2-C , N(SiMe3)Dip 2-N ) stabilized by one electropositive metal fragment L(Cl)Ga] (L=HCC(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)GaSbBN(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. |
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| Keywords: | Antimon ESR-Spektroskopie Hauptgruppenelemente Radikale Röntgenbeugung |
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