Grant Lauren N, Krzystek J, Pinter Balazs, Telser Joshua, Grützmacher Hansjörg, Mindiola Daniel J
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA.
National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310, USA.
Chem Commun (Camb). 2019 May 25;55(42):5966-5969. doi: 10.1039/c9cc01500k. Epub 2019 May 3.
Transmetallation studies with the phosphaethynolate ion, [OCP], have largely resulted in coordination according to classical Lewis acid-base theory. That is, for harder early transition metal ions, O-bound coordination has been observed, whereas in the case of softer late transition metal ions, P-bound coordination predominates. Herein, we report the use of a V(iii) complex, namely [(nacnac)VCl(OAr)] (1) (nacnac = [ArNC(CH)]CH; Ar = 2,6-PrCH), to transmetallate [OCP] and bind via the P-atom as [(nacnac)V(OAr)(PCO)] (2), the first example of a 3d early transition metal that binds [OCP]via the P-atom. Full characterization studies of this molecule including HFEPR spectroscopy, SQuID measurements, and theoretical studies are presented.
使用磷乙炔醇根离子[OCP]进行的金属转移研究在很大程度上是根据经典的路易斯酸碱理论进行配位的。也就是说，对于较硬的早期过渡金属离子，观察到的是与氧结合的配位，而对于较软的晚期过渡金属离子，与磷结合的配位占主导。在此，我们报告了使用一种钒(III)配合物，即[(nacnac)VCl(OAr)] (1)（nacnac = [ArNC(CH)]CH；Ar = 2,6-PrCH），使[OCP]发生金属转移并通过磷原子以[(nacnac)V(OAr)(PCO)] (2)的形式结合，这是首例通过磷原子结合[OCP]的3d早期过渡金属配合物。本文还介绍了对该分子的全面表征研究，包括高频电子顺磁共振光谱、超导量子干涉仪测量和理论研究。
