期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 27, 期 63, 页码 15815-15822出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202103153
关键词
aurophilicity; fluorinated ligands; gold; metallacycles; metal-metal interactions
资金
- Spanish Ministry of Science and Innovation/FEDER [PGC2018-100719-B-100]
- Seneca Foundation of the Region of Murcia (Ayudas a Grupos de Excelencia) [19890/GERM/15]
New dinuclear gold complexes with fluoroalkyl bridging chains were synthesized, and the aurophilic interactions were found to play a crucial role in the complex structures and oxidation reactions. The study extends the understanding and synthesis possibilities of gold complexes.
New dinuclear Au(I), Au(II) and Au(III) complexes containing (CF2)(n) bridging chains were obtained. Metallomacrocycles [Au-2{mu-(CF2)(4)}{mu-diphosphine}] show an uncommon figure-eight structure, the helicity inversion barrier of which is influenced by aurophilic interactions and steric constraints imposed by the diphosphine. Halogenation of LAu(CF2)(4)AuL (L=PPh3, PMe3, (dppf)(1/2), (binap)(1/2)) gave [Au(II)](2) species, some of which display unprecedented folded structures with Au-Au bonds. Aurophilic interactions facilitate this oxidation process by preorganizing the starting [Au(I)](2) complexes and lowering its redox potential. The obtained [Au(II)](2) complexes undergo thermal or photochemical elimination of R3PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.
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