Deegan Meaghan M, Peters Jonas C
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Polyhedron. 2021 Nov 15;209. doi: 10.1016/j.poly.2021.115461. Epub 2021 Sep 4.
The remarkable catalytic transformation of CO to liquid hydrocarbons by Fe and Co catalysts in the industrial Fischer-Tropsch process motivates interest in developing well-defined systems to model aspects of this chemistry. One of the most interesting potential intermediates in this chemistry is a terminally-bound, first row metal carbide, yet a molecular model of this species remains elusive. With this in mind, we targeted the synthesis of highly-activated Fe-thiocarbonyl complexes, as prospective precursors to S-functionalization, C-S bond cleavage, and carbide generation. Herein, we describe the synthesis of three Fe-CS complexes that can be alkylated to generate a series of terminal Fe-carbynes that could be characterized across three oxidation states. Strategies to access C-S bond scission from these species are discussed, including limitations that, thus far, have precluded the generation of a terminal Fe-carbide for this system.
在工业费托合成过程中，铁和钴催化剂可将一氧化碳显著催化转化为液态烃，这激发了人们开发精确体系以模拟该化学过程某些方面的兴趣。这种化学过程中最有趣的潜在中间体之一是末端键合的第一排金属碳化物，但该物种的分子模型仍然难以捉摸。考虑到这一点，我们旨在合成高度活化的铁硫羰基配合物，作为硫官能化、碳硫键断裂和碳化物生成的潜在前体。在此，我们描述了三种铁 - 碳硫配合物的合成，这些配合物可被烷基化以生成一系列末端铁卡宾，它们可在三种氧化态下进行表征。我们还讨论了从这些物种实现碳硫键断裂的策略，包括迄今为止阻碍该体系生成末端铁碳化物的限制因素。
