Change of the Fe Configuration in Chiral Half‐Sandwich Complexes Within the Solvent Cage

Kinetic and Thermodynamic Control of Nitrile Dissociation in the Complexes (RFe,RC)/(SFe,RC)-[CpFe(Prophos)NCR]X (X = I, PF6) by the Inductive Effect

“…There is no preferred orientation of the aryl rings of the nitrile ligands. Including the published structures of ( S Fe , R C )-[CpFe­(Prophos)­NCPh]­X (X = I, PF 6 ) and ( S Fe , R C )-[CpFe­(Prophos)­NC­( p- C 6 H 4 NO 2 )]­PF 6 , the positive torsion angles Cp cent –Fe–C i –C o range between 2 and 137°. , …”

“…Yields, crystallization conditions, spectra, and elemental analysis were published in the Supporting Information of ref .…”

“…Kinetic control affects the ligand substitution reactions and thermodynamic control establishes the equilibrium concentrations of the products. 8,9 The iodide salts are less stable than the PF 6 salts, because the iodide anion is a potential ligand for the unsaturated intermediate (R Fe ,R C )/(S Fe ,R C )-[CpFe(Prophos)] + , formed on dissociation of the Fe−NCR bond. On standing in solution for a longer time or at higher temperatures, the NMR signals of (R Fe ,R C )/(S Fe ,R C )-[CpFe(Prophos)I] show up.…”

Isomerization Processes on Organoruthenium Complexes Bearing κ2(P,C)‐Bidentate Ligands Generated Through Nucleophilic Addition to Coordinated Alkenyl Phosphanes

“…Prochiral alkenes are very useful in enantioselective synthesis Most of the current examples are based in complexes with enantiopure ligands, however the study of transition metal‐fragments bearing a stereogenic center also plays an important role in activating asymmetric olefins towards the addition of nucleophiles in a stereoselective manner . These metal centers usually have a pseudooctaedral geometry that might induce the selective coordination of the prochiral olefins through one of their enantiotopic faces (see Figure ). Moreover, providing that rotation around the C=C bond is allowed, two different rotamers can exist for each of the two isomers.…”

“Chiral-at-Metal” Hemilabile Nickel Complexes with a Latent d10-ML2 Configuration: Receiving Substrates with Open Arms

“…Presently, the development of enantioselective catalysts is almost exclusively ligand-based, and an axiom of ligand design is to move stereogenic elements as close as possible to the metal center. Naturally then, complexes with stereogenic metals have been intensively studied, and the vast majority of them are pseudo-octahedral species stabilized by η 5 -Cp – or η 6 -arene type ligands, , which were used in stereoselective stoichiometric and catalytic transformations. So far, Noyori’s octahedral [Ru I I –BINAP–bis(carboxylato)] and [Ru I I –η 6 -arene– N -tosylethylenediamine] complexes are the most compelling evidence for the effectiveness of stereogenic-at-metal complexes in asymmetric catalysis .…”