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Updated: Mar 21, 2026

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
High Spin Iron-Phosphinidene and Arsinidene Complexes With Attenuated Metal-Ligand Multiple Bond Character
Austin D Chivington1, Álvaro García-Romero1, David C Meier1
1Department of Chemistry, Indiana University, Bloomington, Indiana, USA.
None:
The MEH2 salts (M = Na, K; E = P, As) react with high spin (S = 2) PhB(AdIm)3FeCl (PhB(AdIm)3 - = tris(3-adamantylimidazol-2-ylidene)phenylborate) to afford the corresponding PhB(AdIm)3FePH2 and PhB(AdIm)3FeAsH2 complexes. Remarkably, these complexes can be deprotonated by benzyl potassium in the presence of equimolar 18-crown-6 or 2,2,2-crypt to provide the parent phosphinidene and arsinidene complexes, [PhB(AdIm)3FePH]- and [PhB(AdIm)3FeAsH]-. Structural and spectroscopic characterization, combined with computational investigations, provide evidence for multiconfigurational electronic structures in which the metal-ligand multiple bond character is attenuated by the high spin iron(II) center. Initial reactivity studies reveal the nucleophilic character of the pnictogenidene ligands, which provide phosphinophosphinidene and phosphinoarsinidene products with a chlorodiazaphospholidine electrophile.
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