Anion-Controlled Switching of an X Ligand into a Z Ligand: Coordination Non-innocence of a Stiboranyl Ligand

• Published in: Angewandte Chemie Vol. 126; no. 10; pp. 2671 - 2675
• Main Authors: Ke, Iou-Sheng, Jones, James S., Gabbaï, François P.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03.03.2014; WILEY‐VCH Verlag
• Subjects: Antimon; Fluorid; Ligandendesign; Platin; Strukturaufklärung
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201309132

The tetravalent platinum stiboranyl complex [(o‐(Ph2P)C6H4)2(o‐C6Cl4O2)Sb]PtCl2Ph (2) has been synthesized by reaction of [(o‐(Ph2P)C6H4)2SbClPh]PtCl (1) with o‐chloranil. In the presence of fluoride anions, the stiboranyl moiety of 2 displays non‐innocent behavior and is readily converted into a fluorostiborane unit. This transformation, which is accompanied by elimination of a chloride ligand from the Pt center, results in the formation of [(o‐(Ph2P)C6H4)2(o‐C6Cl4O2)SbF]PtClPh (3). Structural, spectroscopic, and computational studies show that the conversion of 2 into 3 is accompanied by a cleavage of the covalent PtSb bond present in 2 and formation of a longer and weaker Pt→Sb interaction in 3. These results show that this new Pt–Sb platform supports the fluoride‐induced metamorphosis of a stiboranyl X ligand into a stiborane Z ligand. Nicht unschuldig: Ein Austausch von Chlorid gegen Fluorid verwandelt einen Stiboranyl‐X‐Liganden in einen Stiboran‐Z‐Liganden. Das nichtunschuldige Koordinationsverhalten des Antimonliganden manifestiert sich in der Spaltung der kovalenten Sb‐Pt‐Bindung in 1 und der Bildung einer längeren, schwächeren Pt→Sb‐Wechselwirkung in 2, begleitet von einem Farbwechsel.