Access to and Reactivity of Fe 0 , Fe -I , Fe I , and Fe II PC carbene P Pincer Complexes.

Autor: Wang Q; Department of Chemistry, National University of Singapore, Singapore., Manzano RA; Department of Chemistry, National University of Singapore, Singapore., Tinnermann H; Department of Chemistry, National University of Singapore, Singapore., Sung S; Department of Chemistry, National University of Singapore, Singapore., Leforestier B; Department of Chemistry, University of Warwick, UK.; Department of Chemistry, Maynooth University, Ireland., Krämer T; Department of Chemistry, Maynooth University, Ireland., Young RD; Department of Chemistry, National University of Singapore, Singapore.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 Aug 09; Vol. 60 (33), pp. 18168-18177. Date of Electronic Publication: 2021 Jul 09.
DOI: 10.1002/anie.202104130
Abstrakt: Despite their promising metal-ligand cooperative reactivity, PC carbene P pincer ligands are rarely reported for first-row transition-metal centres. Using a dehydration methodology, we report access to an Fe 0 PC carbene P pincer complex (1) that proceeds via an isolated α-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 PC carbene P pincer ligand is also found to stabilize formal Fe II , Fe I , and Fe -I oxidation states, as demonstrated with synthesis and characterization of the complexes [11-X][BAr F 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 Fe I and Fe -I complexes contain significant carbene radical character. The ability of the PC carbene P 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.
(© 2021 Wiley-VCH GmbH.)
Databáze: MEDLINE
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