Rare-Earth Metal Phosphinidene Complexes: A Trip from Bridging One to Terminal One

作者：Qingqing Wen, Bin Feng, Yaofeng Chen · 发表于：Accounts of Chemical Research · 年份：2023 · DOI：10.1021/acs.accounts.3c00429 · 被引用次数：27 · 研究领域：Organometallic Complex Synthesis and Catalysis、Synthesis and characterization of novel inorganic/organometallic compounds、Coordination Chemistry and Organometallics

Conspectus As phosphorus analogues of alkylidene (or carbene) and imido (or nitrene) complexes, phosphinidene complexes have received great attention not only for their fundamental scientific merits but also for their ability to build new phosphorus-containing molecules. A large number of phosphinidene complexes in bridging, mononuclear, or terminal coordination modes have been synthesized, and their reactivity has been extensively explored. However, the synthesis of rare-earth metal (scandium, yttrium, and lanthanide metal) phosphinidene complexes lagged behind the transition metal and actinide congeners for decades. Rare-earth metal ions are among the hardest Lewis acids, whereas phosphinidene ligands are soft Lewis bases; rare-earth metal–phosphinidene coordination is thus mismatched based on the Pearson’s HSAB principle. The bridging rare-earth metal phosphinidene complexes were not reported until 2008, and the synthesis of the mononuclear and terminal species is even more challenging, which has only recently been achieved. Our group reported a bis( μ 2 -phosphinidene)dineodymium complex in 2008. In the following >10 years, we have been pursuing the terminal rare-earth metal phosphinidene complexes. Due to the high instability of rare-earth metal–phosphorus multiple bonds, the synthesis and stabilization of these complexes are extremely difficult. Finally, by using suitable phosphinidene ligands and supporting ligands, we obtained the first mononuclear rare-earth metal ph...