Wang, Qingyang and Manzano, Richard A. and Tinnermann, Hendrik and Sung, Simon and Leforestier, Baptiste and Krämer, Tobias and Young, Rowan D. (2021) Access to and Reactivity of Fe 0 , Fe −I , Fe I , and Fe II PC carbene P Pincer Complexes. Angewandte Chemie, 133 (33). pp. 18316-18325. ISSN 0044-8249

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Abstract

Despite their promising metal–ligand cooperative reactivity, PCcarbeneP pincer ligands are rarely reported for firstrow transition-metal centres. Using a dehydration methodology, we report access to an Fe0 PCcarbeneP pincer complex (1) that proceeds via an isolated a-hydroxylalkyl hydrido complex (3). Reversible carbonyl migration to the carbene position in 1 is found to allow coordination chemistry and E@H bond addition (E = H, B, Cl) across the iron–carbene linkage, representing a unique mechanism for metal–ligand cooperativity. The PCcarbeneP pincer ligand is also found to stabilize formal FeII, Fe I, and Fe@I oxidation states, as demonstrated with synthesis and characterization of the complexes [11-X]-[BArF 20] (X = Br, I), 12, and K[13]. Compound K[13] is found to be highly reactive, and abstracts hydrogen from a range of aliphatic C@H sources. Computational analysis by DFT suggests that the formal FeI and Fe@I complexes contain significant carbene radical character. The ability of the PCcarbeneP ligand scaffold to partake in metal–ligand cooperativity and to support a range of iron oxidation states renders it as potentially useful in many catalytic applications

Item Type:	Article
Additional Information:	Cite as: Q. Wang, R. A. Manzano, H. Tinnermann, S. Sung, B. Leforestier, T. Krämer, R. D. Young, Angew. Chem. 2021, 133, 18316.
Keywords:	PCcarbeneP pincer ligands; Reactivity of Fe 0;PCcarbeneP
Academic Unit:	Faculty of Science and Engineering > Chemistry Faculty of Science and Engineering > Research Institutes > Hamilton Institute
Item ID:	17438
Identification Number:	https://doi.org/10.1002/ange.202104130
Depositing User:	Tobias Kraemer
Date Deposited:	17 Aug 2023 11:12
Journal or Publication Title:	Angewandte Chemie
Publisher:	Wiley on line
Refereed:	Yes
URI:	Publisher
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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