Hernandez Shirley, Belov Dmitry S, Krivovicheva Vasilisa, Senthil Shuruthi, Bukhryakov Konstantin V
Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States.
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
J Am Chem Soc. 2024 Jul 17;146(28):18905-18909. doi: 10.1021/jacs.4c07588. Epub 2024 Jul 5.
Preserving vanadium in a high oxidation state during chemical transformations can be challenging due to the oxidizing nature of V(+5) species. Oxo and similar isoelectronic ligands have been utilized to stabilize V(+5) by extensive π-donation. However, decreasing the bond order between V and the oxo ligand often results in a reduction of the metal center. Herein, we report a unique transformation involving anionic V(+5) alkylidene that converts a V(+5) oxo complex to a V(+5) alkylidyne in three steps without altering the oxidation state of the metal center. This method has been used to obtain rare 3d Schrock carbynes, which provide easy and scalable access to V(+5) alkylidynes.
在化学转化过程中，由于V(+5)物种的氧化性，保持钒处于高氧化态具有挑战性。氧代和类似的等电子配体已被用于通过广泛的π-供体作用来稳定V(+5)。然而，降低V与氧代配体之间的键级通常会导致金属中心的还原。在此，我们报道了一种独特的转化过程，涉及阴离子V(+5)亚烷基，该过程可在不改变金属中心氧化态的情况下，分三步将V(+5)氧代配合物转化为V(+5)次烷基。该方法已用于获得稀有的3d施罗克卡宾，从而为V(+5)次烷基提供了简便且可扩展的合成途径。
