Journal article
Halogen-Bonding-Assisted Iodosylbenzene Activation by a Homogenous Iron Catalyst
The iron(III) complex of hexadentate N,N,N′-tris(2-pyridylmethyl)ethylendiamine-N′-acetate (tpena−) is a more effective homogenous catalyst for selective sulfoxidation and epoxidation with insoluble iodosylbenzene, [PhIO]n, compared with soluble methyl-morpholine-N-oxide (NMO). We propose that two molecules of [Fe(tpena)]2+ cooperate to solubilize PhIO, extracting two equivalents to form the halogen-bonded dimeric {[Fe(tpena)OIPh]2}4+.
The closest intradimeric I⋅⋅⋅O distance, 2.56 Å, is nearly 1 Å less than the sum of the van de Waals radii of these atoms. A correlation of the rates of the reaction of {[Fe(tpena)OIPh]2}4+ with para-substituted thioanisoles indicate that this species is a direct metal-based oxidant rather than a derived ferryl or perferryl complex.
A study of gas-phase reactions indicate that an ion at m/z=231.06100 originates from solution-state {[Fe(tpena)OIPh]2}4+ and is ascribed to [FeIII(tpenaO)]2+, derived from an intramolecular O atom insertion into an Fe–tpena donor bond. Proposed ion pairs, {[Fe(tpena)OIPh]Cl}+ and {[Fe(tpena)OIPh]ClO4}+, are more stable than native [Fe(tpena)OIPh]2+ ions, suggesting that halogen-bonding, as for the solution and solid states, operates also in the gas phase.
Language: | English |
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Year: | 2016 |
Pages: | 3810-3820 |
ISSN: | 15213765 and 09476539 |
Types: | Journal article |
DOI: | 10.1002/chem.201503112 |
ORCIDs: | Frandsen, Cathrine |
Catalysts Chemical bonds Chemical reactions Chemistry (all) Chlorine Epoxidation Gas Phase Chemistry Gas phase chemistry Gas-phase chemistry Gas-phase reactions Gases Halogen Bonding Halogen bonding Halogen-bonding Hexadentate Homogenous catalyst Iodosylbenzene Ions Iron Iron catalyst Iron compounds Oxidation Phase interfaces Reaction rates Sulfoxidation
epoxidation gas-phase chemistry halogen-bonding iodosylbenzene iron sulfoxidation