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Reactivity of Xantphos‐Type Rhodium Complexes Towards SF 4 : SF 3 Versus SF 2 Complex Generation
Author(s) -
Wozniak Martin,
Sander Stefan,
Cula Beatrice,
Ahrens Mike,
Braun Thomas
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200626
Subject(s) - chemistry , rhodium , cationic polymerization , dimethylamine , medicinal chemistry , reactivity (psychology) , allene , chloromethane , xantphos , stereochemistry , catalysis , palladium , organic chemistry , medicine , alternative medicine , pathology
S−F‐bond activation of sulfur tetrafluoride at [Rh(Cl)( t Bu xanPOP)] ( 1 ; t Bu xanPOP=9,9‐dimethyl‐4,5‐bis‐(di‐tert‐butylphosphino)‐xanthene) led to the formation of the cationic complex [Rh(F)(Cl)(SF 2 )( t Bu xanPOP)][SF 5 ] ( 2 a ) together with trans‐ [Rh(Cl)(F) 2 ( t Bu xanPOP)] ( 3 ) and cis‐ [Rh(Cl) 2 (F)( t Bu xanPOP)] ( 4 ) which both could also be obtained by the reaction of SF 5 Cl with 1 . In contrast to that, the conversion of SF 4 at the methyl complex [Rh(Me)( t Bu xanPOP)] ( 5 ) gave the isolable and room‐temperature stable cationic λ 4 ‐trifluorosulfanyl complex [Rh(Me)(SF 3 )( t Bu xanPOP)][SF 5 ] ( 6 ). Treatment of 6 with the Lewis acids BF 3 or AsF 5 produced the dicationic difluorosulfanyl complex [Rh(Me)(SF 2 )( t Bu xanPOP)][BF 4 ] 2 ( 8 a ) or [Rh(Me)(SF 2 )( t Bu xanPOP)][AsF 6 ] 2 ( 8 b ), respectively. Refluorination of 8 a was possible with the use of dimethylamine giving [Rh(Me)(SF 3 )( t Bu xanPOP)][BF 4 ] ( 9 ). A reaction of 6 with trichloroisocyanuric acid (TClCA) gave the fluorido complex [Rh(F)(Cl)(SF 2 )( t Bu xanPOP)][Cl] ( 2 b ) together with chloromethane and SF 5 Cl.