ISCR (Institut des Sciences Chimiques de Rennes)─UMR 6226, Université de Rennes, CNRS, 263 av. du général Leclerc, F-35042 Rennes, France.
LCPNO, CNRS & INSA, Université de Toulouse, 135 avenue de Rangueil, F-31077 Toulouse, France.
Inorg Chem. 2023 May 15;62(19):7250-7263. doi: 10.1021/acs.inorgchem.3c00045. Epub 2023 May 2.
The palladium-catalyzed annulation reaction of alkynes enables an attractive approach to siloles. Their access from silirenes and terminal alkynes proved rather general, involving reactive intermediates that have remained elusive to date. Starting from 1,2-bis(3-thienyl)silirene as a source of photochromic siloles, the mechanism of the annulation reaction has been revisited, and palladasilacyclobutenes resulting from the activation of the silirene could be isolated and thoroughly characterized (NMR, X-ray, and DFT). Their role as reactive intermediates and their fate in the course of the reaction were also studied in situ. In combination with in-depth DFT calculations, a clearer picture of the mechanism and the reactive key species is disclosed.
钯催化炔烃的环化反应为硅咯提供了一种很有吸引力的方法。它们可以通过硅雷林和末端炔烃来制备，这一方法具有广泛的适用性，涉及到目前仍难以捉摸的反应中间体。以作为光致变色硅咯来源的 1,2-双(3-噻吩基)硅雷林为起点，重新研究了环化反应的机理，并可以分离和彻底表征得到的钯杂硅环丁烯（NMR、X 射线和 DFT）。还原位研究了它们作为反应中间体的作用及其在反应过程中的命运。结合深入的 DFT 计算，揭示了更清晰的反应机理和反应关键物种的图像。
