In:
Angewandte Chemie International Edition, Wiley, Vol. 60, No. 33 ( 2021-08-09), p. 18168-18177
Abstract:
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.
Type of Medium:
Online Resource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.202104130
Language:
English
Publisher:
Wiley
Publication Date:
2021
detail.hit.zdb_id:
2011836-3
detail.hit.zdb_id:
123227-7
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