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Reactivity of Xantphos-Type Rhodium Complexes Towards SF4 : SF3 Versus SF2 Complex Generation.

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.

SUBMITTER: Wozniak M 

PROVIDER: S-EPMC9322540 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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Reactivity of Xantphos-Type Rhodium Complexes Towards SF<sub>4</sub> : SF<sub>3</sub> Versus SF<sub>2</sub> Complex Generation.

Wozniak Martin M   Sander Stefan S   Cula Beatrice B   Ahrens Mike M   Braun Thomas T  

Chemistry (Weinheim an der Bergstrasse, Germany) 20220504 33

S-F-bond activation of sulfur tetrafluoride at [Rh(Cl)(<sup>tBu</sup> xanPOP)] (1; <sup>tBu</sup> xanPOP=9,9-dimethyl-4,5-bis-(di-tert-butylphosphino)-xanthene) led to the formation of the cationic complex [Rh(F)(Cl)(SF<sub>2</sub> )(<sup>tBu</sup> xanPOP)][SF<sub>5</sub> ] (2 a) together with trans-[Rh(Cl)(F)<sub>2</sub> (<sup>tBu</sup> xanPOP)] (3) and cis-[Rh(Cl)<sub>2</sub> (F)(<sup>tBu</sup> xanPOP)] (4) which both could also be obtained by the reaction of SF<sub>5</sub> Cl with 1. In contr  ...[more]

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