Heterolytic C–O cleavage in arylethers activated by [Fe(η⁵-C₅H₅)]⁺

Abstract

The C-0 bond of Fe(q5-C5H5)+ complexes of aryl ethers is cleaved smoothly by reaction of ButOK in THF or KOH in DME, yielding n-phenate complexes; transetherification can also be achieved in situ at room temperature.

Activation of Simple Arenes by the CpFe + Group and Applications to the Synthesis of Dendritic Molecular Batteries

“…Serendipitously, we found that KOH or tBuOK under very mild conditions easily cleaved the iron complexes of aromatic ethers. The activating CpFe þ group again induces this reaction, which is very general for a variety of aromatic ether complexes (Scheme 22) [67,68].…”

Phenolate Complexes of Iron(II) in Different Spin States

“…The carbon atoms of the six‐membered ring show five bond lengths to the iron center ranging from 2.056(2) Å (FeC54) to 2.252(3) Å (FeC52) while the carbonyl carbon atom is found at a nonbonding distance of 2.414(3) Å from the iron center. The fold angle of the six‐membered ring along the line C52⋅⋅⋅C56 is 9.5°, whereas for related complexes, fold angles of [Cp*Fe(η 5 ‐C 6 H 5 O)] 1.6°,6 (Cp*=η 5 ‐C 5 Me 5 ) for [Cp*Ir(η 5 ‐C 6 H 5 O)] + 21°,7 for [Cp*Rh(η 5 ‐C 6 H 5 O)] + 14°,8 for [Cp*Ru(η 5 ‐C 6 H 5 O)] 4°,9 for [Cp*Ru(η 5 ‐2,6‐ t Bu 2 OC 6 H 3 )] 19.1°10 and for [(OC) 3 Mn(η 5 ‐C 6 H 5 O)] 21.3°11 have been determined.…”

Synthesis of (η6-arene)(η5-cyclopentadienyl) iron (II) complexes with heteroatom and carbonyl substituents. Part I: Oxygen and carbonyl substituents

“…The advent of a simple method of heterolytic C-O bond cleavage in arylether complexes to give p phenate complexes [9] should prove useful in the case of the 1,3,5-trimethoxybenzene complex and would result in the formation of an important template for the synthesis of polymeric ArFeCp compounds [10]. The corresponding methoxy-and 1,2-dimethoxybenzene complexes were obtained in 35% and 32% yields, respectively.…”