Leiby Ian S, Parparcén Virginia, Ding Natalya, Kunz Klara J, Wolfarth Sadie A, Stevens Jeremiah E, Nataro Chip
Department of Chemistry, Lafayette College, Easton, PA 18045, USA.
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210, USA.
Molecules. 2024 Apr 29;29(9):2047. doi: 10.3390/molecules29092047.
The addition of Na[BArF] (BArF = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) to [Pd(PP)Cl] (PP = 1,1'-bis(phosphino)ferrocene ligands) compounds results in the loss of a chloride ligand and the formation of the dimeric species [Pd(PP)(-Cl)][BArF]. In most cases, the addition of a monodentate phosphine, PR, to these dimeric species leads to cleaving of the dimer and formation of [Pd(PP)(PR)Cl][BArF]. While these reactions are readily observed via a significant color change, the P{H} NMR spectra offer more significant support, as the singlet for the dimer is replaced with three doublets of doublets. The reaction seems to take place for a wide range of PR ligands, although there do appear to be steric limitations to the reaction. The compounds were thoroughly characterized by NMR, and X-ray crystal structures of several of the compounds were obtained. In addition, the ferrocenyl backbone of the 1,1'-bis(phosphino)ferrocene ligands provides an opportunity to examine the oxidative electrochemistry of these compounds. In general, the potential at which oxidations of these compounds occurs shows a dependence on the phosphine substituents.
向[Pd(PP)Cl]（PP = 1,1'-双（膦基）二茂铁配体）化合物中加入Na[BArF]（BArF = 四（3,5-双（三氟甲基）苯基）硼酸根）会导致一个氯配体的离去，并形成二聚体物种[Pd(PP)(-Cl)][BArF]。在大多数情况下，向这些二聚体物种中加入单齿膦PR会导致二聚体裂解并形成[Pd(PP)(PR)Cl][BArF]。虽然这些反应通过显著的颜色变化很容易观察到，但磷的核磁共振谱提供了更有力的支持，因为二聚体的单峰被三个双二重峰取代。尽管该反应似乎对多种PR配体都能发生，但反应似乎确实存在空间位阻限制。这些化合物通过核磁共振进行了全面表征，并获得了其中几种化合物的X射线晶体结构。此外，1,1'-双（膦基）二茂铁配体的二茂铁骨架为研究这些化合物的氧化电化学提供了机会。一般来说，这些化合物发生氧化的电位显示出对膦取代基的依赖性。
