期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 37, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202207760
关键词
Ligand Design; Perfluoro Compounds; Rhodacycle; Rhodium; Structure Elucidation
In this study, perfluororhodacyclopentane was successfully prepared using a PBP pincer ligand. The perfluororhodacyclopentane showed high reactivity towards hydrogenolysis, iodinolysis, and protonolysis due to the strong trans-effect of the boryl ligand. This study also demonstrated the potential application of the PBP pincer skeleton in the preparation of fluorinated compounds from TFE.
Perfluororhodacyclopentane supported by PBP pincer ligand PBP-Rh-III(CF2)(4) (2) was prepared from PBP-Rh-I-PPh3 (1) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh-C-F bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M-C-F bonds of perfluorometallacyclopentanes are known to be very stable, 2 shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans-effect of the highly sigma-donating boryl ligand. Analogous PCP pincer complex PCP-Rh-III(CF2)(4) (4) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh-C-F bond. Catalytic production of 1,1,2,2,3,3,4,4-octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh-C-F bonds. This report demonstrates the possible application of PBP-pincer skeleton to the preparation of fluorinated compounds from TFE.
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