New Concepts for Designing d10‐M(L)n Catalysts: d Regime,s Regime and Intrinsic Bite‐Angle Flexibility

Our aim is to understand the electronic and steric factors that determine the activity and selectivity of transition‐metal catalysts for cross‐coupling reactions. To this end, we have used the activation strain model to quantum‐chemically analyze the activity of catalyst complexes d¹⁰‐M(L)_n toward methane C?H oxidative addition. We studied the effect of varying the metal center M along the nine d¹⁰ metal centers of Groups 9, 10, and 11 (M=Co^?, Rh^?, Ir^?, Ni, Pd, Pt, Cu⁺, Ag⁺, Au⁺), and, for completeness, included variation from uncoordinated to mono‐ to bisligated systems (n=0, 1, 2), for the ligands L=NH₃, PH₃, and CO. Three concepts emerge from our activation strain analyses: 1) bite‐angle flexibility, 2) d‐regime catalysts, and 3) s‐regime catalysts. These concepts reveal new ways of tuning a catalyst’s activity. Interestingly, the flexibility of a catalyst complex, that is, its ability to adopt a bent L‐M‐L geometry, is shown to be decisive for its activity, not the bite angle as such. Furthermore, the effect of ligands on the catalyst’s activity is totally different, sometimes even opposite, depending on the electronic regime (d or s) of the d¹⁰‐M(L)_n complex. Our findings therefore constitute new tools for a more rational design of catalysts.     

Fe or FeNO Catalysis? A Quantum Chemical Investigation of the [Fe(CO)3(NO)]−‐Catalyzed Cloke–Wilson Rearrangement

A quantum chemical investigation of the Bu₄N[Fe(CO)₃(NO)]‐catalyzed Cloke–Wilson rearrangement of vinyl cyclopropanes is reported. It was found that allylic C?C bond activation can proceed through a S_N2′ or S_N2‐type mechanism. The application of the recently reported intrinsic bond orbital (IBO) method for all structures indicated that one Fe?N π bond is directly involved. Further analysis showed that during the reaction oxidation occurs at the NO ligand exclusively.     

On the Reaction Mechanism of the Complete Intermolecular O2 Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

The recently described intermolecular O₂ transfer between the side‐on Ni‐O₂ complex [(12‐TMC)Ni‐O₂]⁺ and the manganese complex [(14‐TMC)Mn]²⁺, where 12‐TMC and 14‐TMC are 12‐ and 14‐membered macrocyclic ligands, 12‐TMC=1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane and 14‐TMC=1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long‐range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two‐step reaction, with a first rate‐determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a μ‐η¹:η¹‐O₂ coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction.     

Palladium–N‐Heterocyclic Carbene (NHC)‐Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp3)H Activation: Scope and DFT Study

Two bulky, chiral, monodentate N‐heterocyclic carbene ligands were applied to palladium‐catalyzed asymmetric C?H arylation to incorporate C(sp³)?H bond activation. Racemic mixtures of the carbamate starting materials underwent regiodivergent reactions to afford different trans‐2,3‐substituted indolines. Although this C_Ar?C_alkyl coupling requires high temperatures (140–160 °C), chiral induction is high. This regiodivergent reaction, when carried out with enantiopure starting materials, can lead to single structurally different enantiopure products, depending on the catalyst chirality. The C?H activation at a tertiary center was realized only in the case of a cyclopropyl group. No C?H activation takes place alpha to a tertiary center. A detailed DFT study is included and analyses of methyl versus methylene versus methine C?H activation is used to rationalize experimentally observed regio‐ and enantioselectivities.     

Aryl‐Copper(III)‐Acetylides as Key Intermediates in CCsp Model Couplings under Mild Conditions

The mechanism of copper‐mediated Sonogashira couplings (so‐called Stephens–Castro and Miura couplings) is not well understood and lacks clear comprehension. In this work, the reactivity of a well‐defined aryl‐Cu^III species ( 1 ) with p‐R‐phenylacetylenes (R=NO₂, CF₃, H) is reported and it is found that facile reductive elimination from a putative aryl‐Cu^III‐acetylide species occurs at room temperature to afford the C_aryl?C_sp coupling species ( I_R ), which in turn undergo an intramolecular reorganisation to afford final heterocyclic products containing 2H‐isoindole ( P , P , P_Ha ) or 1,2‐dihydroisoquinoline ( P_Hb ) substructures. Density Functional Theory (DFT) studies support the postulated reductive elimination pathway that leads to the formation of C?C_sp bonds and provide the clue to understand the divergent intramolecular reorganisation when p‐H‐phenylacetylene is used. Mechanistic insights and the very mild experimental conditions to effect C_aryl?C_sp coupling in these model systems provide important insights for developing milder copper‐catalysed C_aryl?C_sp coupling reactions with standard substrates in the future.     

Transalkylation of Higher Trifluoromethylated Fullerenes with C70: A Pathway to New Addition Patterns of C70(CF3)8

We report three new isomers of C₇₀(CF₃)₈, structurally related to p⁷mp‐C₇₀(CF₃)₁₀, that are inaccessible by direct trifluoromethylation, but can be easily identified among the products of the transalkylation of higher trifluoromethylfullerenes with C₇₀. The reported compounds are characterized by UV/Vis, 1 D and 2 D COSY ¹⁹F NMR spectroscopy, and DFT calculations. A rather unusual addition pattern is observed in p⁶,i‐C₇₀(CF₃)₈ in which one addend is attached remotely from the others; polarization of the adjacent unsaturated bonds by the addend makes the molecule readily oxidizable.     

Aromatic Superhalogens

No organic molecules with electron affinities near or above those of halogens are known. We show for the first time that aromaticity rules can be used to design molecules with electron affinities far exceeding those of halogen atoms either by tailoring the ligands of cyclopentadienyl or by multiple benzoannulations of cyclopentadienyl in conjunction with the substitution of CH groups with isoelectronic N atoms. Results based on density functional theory revealed that the electron affinities of some of these organic molecules can reach as high as 5.59 eV, thus opening the door to new class of superhalogens that contain neither a metal nor a halogen atom.     

Phase‐Transfer‐Catalysed Synthesis of Pyrroloindolines and Pyridoindolines by a Hydrogen‐Bond‐Assisted Isocyanide Cyclization Cascade

A cascade reaction that generates pyrrolo‐ and pyridoindoline motifs from isocyanide precursors under phase‐transfer conditions is described. This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all‐carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5‐endo dig cyclization, rather than an anionic 6π electrocyclization. Investigations employing chiral phase‐transfer catalysts have given promising selectivities to date.