Iron-catalyzed cross-coupling reactions have an outstanding potential for sustainable organic synthesis, but remain poorly understood mechanistically. Here, we use electrospray-ionization (ESI) mass spectrometry to identify the ionic species formed in these reactions and characterize their reactivity. Transmetalation of Fe(acac) (acac=acetylacetonato) with PhMgCl in THF (tetrahydrofuran) produces anionic iron ate complexes, whose nuclearity (1 to 4 Fe centers) and oxidation states (ranging from -I to +III) crucially depend on the presence of additives or ligands. Upon addition of iPrCl, formation of the heteroleptic Fe complex [Ph Fe(iPr)] is observed. Gas-phase fragmentation of this complex results in reductive elimination and release of the cross-coupling product with high selectivity.
We have applied a combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, and Mössbauer spectroscopy to identify and characterize the organoferrate species R Fe formed upon the transmetalation of iron precursors (Fe(acac), FeCl, FeCl, Fe(OAc)) with Grignard reagents RMgX (R = Me, Et, Bu, Hex, Oct, Dec, MeSiCH, Bn, Ph, Mes, 3,5-(CF)-CH; X = Cl, Br) in tetrahydrofuran. The observed organoferrates show a large variety in their aggregation (1 ≤ m ≤ 8) and oxidation states (I to IV), which are chiefly determined by the nature of their organyl groups R. In numerous cases, the addition of a bidentate amine or phosphine changes the distributions of organoferrates and affects their stability. Besides undergoing efficient intermolecular exchange processes, several of the probed organoferrates react with organyl (pseudo)halides R'X (R' = Et, Pr, Bu, Ph, p-Tol; X = Cl, Br, I, OTf) to afford heteroleptic complexes of the type RFeR'. Gas-phase fragmentation of most of these complexes results in reductive eliminations of the coupling products RR' (or, alternatively, of R). This finding indicates that iron-catalyzed cross-coupling reactions may proceed via such heteroleptic organoferrates RFeR' as intermediates. Gas-phase fragmentation of other organoferrate complexes leads to β-hydrogen eliminations, the loss of arenes, and the expulsion of organyl radicals. The operation of both one- and two-electron processes is consistent with previous observations and contributes to the formidable complexity of organoiron chemistry.
Substitution reactions between gaseous ions and neutral substrate molecules are of ongoing high interest. To investigate these processes in a qualitative and quantitative manner, we have constructed a device, with which a defined amount of a volatile substrate can be mixed with a defined amount of helium gas and added into a three‐dimensional quadrupole ion trap. From the known inner volume of the device, the known ratio nsubstrate:nHe of the mixture, and the determined absolute partial pressure of helium in the ion trap, we can derive the partial pressure of the substrate in the ion trap and, thus, convert the directly observable pseudo–first‐order rate constants of the substitution reactions into absolute bimolecular rate constants. We have tested the device by investigating a series of SN2 reactions of Br− and CF3CH2O− anions as well as ligand exchange reactions of ligated Na+ cations. As the obtained results suggest, the described device makes it possible to determine the bimolecular rate constants of substitution reactions as well as other ion‐molecule reactions with satisfactory accuracy and reliability.
A combination of electrospray-ionization mass spectrometry and Mössbauer spectroscopy was used to investigate the species generated in situ in highly enantioselective Fe/NHC-catalyzed C–H alkylations.
Iron-catalyzed cross-coupling reactions provide a promising way to form new carbon–carbon bonds and build up molecular complexity. This short review presents recent advances in the synthetic application of these reactions as well as in the elucidation of their mechanism. It also highlights remaining problems and aims at pointing out ways toward possible remedies.1 Introduction2 Synthesis: Recent Accomplishments and Unsolved Problems2.1 Substrate Scope: Electrophiles2.2 Substrate Scope: Nucleophiles2.3 Catalyst Activity and Chemoselectivity2.4 Stereoselectivity2.5 Practical Aspects3 Mechanism: Recent Insights and Open Questions3.1 Transmetallation and Activation of the Iron Precatalyst3.2 Coupling via Oxidative Addition and Reductive Elimination3.3 Coupling via C–X Bond Homolysis and Radical Rebound3.4 Coupling via Bimolecular C–X Bond Homolysis3.5 Other Reactions of Organoiron Species with Electrophiles4 Toward Rational Reaction Improvement5 Conclusion
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