Spinnato Davide, Moon Hye Won, Leutzsch Markus, Nöthling Nils, Cornella Josep
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
Organometallics. 2025 Aug 20;44(17):1888-1892. doi: 10.1021/acs.organomet.5c00260. eCollection 2025 Sep 8.
Herein, we describe a unique example of a low-valent monocoordinated Bi-(I) complex acting as a Lewis base partner in a FLP activation reaction. The interplay between a bulky and rigid Bi-(I) and the Lewis acidic tris-(pentafluorophenyl)-borane (BCF) enables the opening of tetrahydrofuran (THF), delivering a zwitterionic Bi-(+)/B(-) product, which could be isolated and characterized spectroscopically and through SC-XRD. The zwitterionic bismuth complex exhibits remarkable spectroscopic features in the visible range, namely an LMCT band corresponding to the transition from the aromatic fluorene to the highly electron-poor cationic bismuth center. Interestingly, excitation of this band results in ring-closing C-O bond formation and subsequent recovery of the Bi-(I), thus constituting a photoreversible FLP activation with bismuth.
在此，我们描述了一个独特的例子，即低价单配位铋（I）配合物在氟化物活化反应中作为路易斯碱伙伴。庞大且刚性的铋（I）与路易斯酸性三（五氟苯基）硼烷（BCF）之间的相互作用使得四氢呋喃（THF）开环，生成一种两性离子Bi(+)/B(-)产物，该产物可通过光谱法以及单晶X射线衍射（SC-XRD）进行分离和表征。这种两性离子铋配合物在可见光范围内展现出显著的光谱特征，即对应于从芳族芴到高度缺电子阳离子铋中心跃迁的配体到金属的电荷转移（LMCT）带。有趣的是，该带的激发导致环合C-O键形成以及随后铋（I）的恢复，从而构成了铋介导的光可逆氟化物活化。
