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

被引：5
|
作者：
Wozniak, Martin [1 ]
Sander, Stefan [1 ]
Cula, Beatrice [1 ]
Ahrens, Mike [1 ]
Braun, Thomas [1 ]
机构：
[1] Humboldt Univ, Dept Chem, Brook Taylor Str 2, D-12489 Berlin, Germany
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2022年 / 28卷 / 33期
关键词：
fluorido complexes; rhodium; S-F activation; sulfur fluorides; sulfur tetrafluoride; H BOND ACTIVATION; C-H; FLUORINATION; DERIVATIVES; BIFLUORIDE; CHEMISTRY; FLUORIDE; CONVERSION; PHOSPHINE; BIS;
D O I：
10.1002/chem.202200626
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
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 SF5Cl 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 lambda(4)-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 SF5Cl.
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页数：8
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