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Published November 15, 2021 | Accepted Version
Journal Article Open

Synthesis and functionalization reactivity of Fe-thiocarbonyl and thiocarbyne complexes

Abstract

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.

Additional Information

© 2021 Published by Elsevier. Received 14 June 2021, Revised 22 August 2021, Accepted 31 August 2021, Available online 4 September 2021. We acknowledge the NIH (GM-075757) for financial support, as well as the X-Ray Crystallography Facility in the Beckman Institute at Caltech, which is supported by the Dow Next Generation Instrumentation Grant/Educator Funds. We additionally thank Mike Takase, Larry Henling, and Nina Gu for experimental assistance. CRediT authorship contribution statement: Meaghan M. Deegan: Conceptualization, Data curation, Formal analysis. Jonas C. Peters: Conceptualization, Formal analysis. The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Created:
August 22, 2023
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October 23, 2023