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Updated: Jul 19, 2025
Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
FeII complexes supported by an iminophosphorane ligand: synthesis and reactivity
Thibault Tannoux1, Louis Mazaud1, Thibault Cheisson1
1Laboratoire de Chimie Moléculaire (LCM) CNRS, Ecole Polytechnique, Institut Polytechnique de Paris, Route de Saclay, F-91120 Palaiseau Cedex, France. audrey.auffrant@polytechnique.edu.
Abstract:
The synthesis of iron complexes supported by a mixed phosphine-lutidine-iminophosphorane (PPyNP) ligand was carried out. While bidentate κ2-N,N coordination was observed for FeCl2, pincer coordination modes were adopted at cationic iron centers, either through dechlorination of [LFe(PPyNP)Cl2] (1) or direct coordination of PPyNP to Fe(OTf)2. Reaction with tert-butylisocyanide gave access to the diamagnetic octahedral complex [Fe(PPyNP)(CNtBu)3]X2 (X = OTf (4), Cl (4')). Both 1 and 4 were shown to undergo deprotonation of the phosphinomethyl group, but the resulting complexes were not active for the dehydrogenative coupling of hexan-1-ol. The hydrosilylation of acetophenones was catalyzed at room temperature with 1 mol% of a catalyst generated in situ from cationic PPyNP-supported iron triflate complexes and KHBEt3.
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