Deegan Meaghan M, Peters Jonas C
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Chem Commun (Camb). 2019 Aug 7;55(64):9531-9534. doi: 10.1039/c9cc04032c.
Despite efforts toward extending multiple bonding motifs to late metal systems, examples of late transition metal carbynes remain scarce. Herein, we describe the synthesis of a series of L3Co(CO) complexes supported by a trisphosphine ligand framework, with the most reduced of these complexes being amenable to O-functionalization. This transformation provides access to the second reported example of a terminal Co-carbyne complex, in this case stabilized in a pseudotetrahedral geometry (i.e., L3Co[triple bond, length as m-dash]C-OSiR3). Its geometry makes its electronic structure suitable for comparison to structurally-related examples of terminal Co-imido and oxo species.
尽管人们努力将多种成键模式扩展到后过渡金属体系，但后过渡金属卡宾的实例仍然很少。在此，我们描述了一系列由三膦配体框架支撑的L3Co(CO)配合物的合成，其中还原程度最高的这些配合物易于进行O-官能化。这种转化提供了第二个被报道的末端钴卡宾配合物的实例，在这种情况下，它以假四面体几何构型（即L3Co≡C-OSiR3）稳定存在。其几何构型使其电子结构适合与末端钴亚胺和氧代物种的结构相关实例进行比较。
