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Access to and Reactivity of Fe 0 , Fe −I , Fe I , and Fe II PC carbene P Pincer Complexes
Author(s) -
Wang Qingyang,
Manzano Richard A.,
Tinnermann Hendrik,
Sung Simon,
Leforestier Baptiste,
Krämer Tobias,
Young Rowan D.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202104130
Subject(s) - carbene , pincer movement , chemistry , reactivity (psychology) , ligand (biochemistry) , cooperativity , pincer ligand , catalysis , transition metal carbene complex , medicinal chemistry , organometallic chemistry , metal , stereochemistry , crystallography , photochemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
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.