Mixed-Valence Iron Complexes Containing End-On Bridging Cyaphide Ions

J Am Chem Soc. 2024 Oct 23;146(42):29207-29213. doi: 10.1021/jacs.4c11741. Epub 2024 Oct 8.

Abstract

Iron cyanide compounds are among the oldest known synthetic coordination compounds, dating back to the early 18th century. By contrast, iron complexes of the cyaphide ion (C≡P-)─a heavy valence isoelectronic analog of the cyanide ion─are unknown. Herein we report the synthesis of highly stable mono- and bis-cyaphide complexes of iron(II), namely Fe(depe)2(Cl)(CP) and Fe(depe)2(CP)2 (depe = 1,2-bis(diethylphosphino)ethane). These iron(II) cyaphide complexes are capable of further coordination to iron(I) in a hitherto unknown linear coordination geometry, affording the conjugated multimetallic mixed-valence complexes [{Fe(depe)2}2(μ-CP)(N2)][BArF4]2 and [{Fe(depe)2}3(μ-CP)2][OTf]2.