Related Experiment Video
Updated: Sep 27, 2025

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Reactivity of Xantphos-Type Rhodium Complexes Towards SF4 : SF3 Versus SF2 Complex Generation
Martin Wozniak1, Stefan Sander1, Beatrice Cula1
1Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany.
Abstract:
S-F-bond activation of sulfur tetrafluoride at [Rh(Cl)(tBu xanPOP)] (1; tBu xanPOP=9,9-dimethyl-4,5-bis-(di-tert-butylphosphino)-xanthene) led to the formation of the cationic complex [Rh(F)(Cl)(SF2 )(tBu xanPOP)][SF5 ] (2 a) together with trans-[Rh(Cl)(F)2 (tBu xanPOP)] (3) and cis-[Rh(Cl)2 (F)(tBu xanPOP)] (4) which both could also be obtained by the reaction of SF5 Cl with 1. In contrast to that, the conversion of SF4 at the methyl complex [Rh(Me)(tBu xanPOP)] (5) gave the isolable and room-temperature stable cationic λ4 -trifluorosulfanyl complex [Rh(Me)(SF3 )(tBu xanPOP)][SF5 ] (6). Treatment of 6 with the Lewis acids BF3 or AsF5 produced the dicationic difluorosulfanyl complex [Rh(Me)(SF2 )(tBu xanPOP)][BF4 ]2 (8 a) or [Rh(Me)(SF2 )(tBu xanPOP)][AsF6 ]2 (8 b), respectively. Refluorination of 8 a was possible with the use of dimethylamine giving [Rh(Me)(SF3 )(tBu xanPOP)][BF4 ] (9). A reaction of 6 with trichloroisocyanuric acid (TClCA) gave the fluorido complex [Rh(F)(Cl)(SF2 )(tBu xanPOP)][Cl] (2 b) together with chloromethane and SF5 Cl.
Related Concept Videos
Preparation and Reactions of Sulfides
Radical Reactivity: Intramolecular vs Intermolecular
Preparation and Reactions of Thiols
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
Hybridization of Atomic Orbitals II

![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)