Mechanistic analysis of iridium(III) catalyzed direct C-H arylations: a DFT study

In a recent experimental work the Ir complex [Ir(cod)(py)(PCy(3))](PF(6)) (that is, Crabtree's catalyst) has been shown to catalyze the C-H arylation of electron-rich heteroarenes with iodoarenes using Ag(2)CO(3) as base. For this process, an electrophilic metalation mechanism, (S(E)Ar) has been proposed as operative mechanism rather than the concerted metalation-deprotonation (CMD) mechanism, widely implicated in Pd-catalyzed arylation reactions. Herein we have investigated the C-H activation step for several (hetero)arenes catalyzed by a Ir(III) catalyst and compared the data obtained with the results for the Pd(II)-catalyzed C-H bond activation. The calculations demonstrate that, similar to Pd(II)-catalyzed reactions, the Ir(III)-catalyzed direct C-H arylation occurs through the CMD pathway which accounts for the experimentally observed regioselectivity. The transition states for Ir(III)-catalyzed direct C-H arylation feature stronger metal-C((arene)) interactions than those for Pd(II)-catalyzed C-H arylation. The calculations also demonstrate that ligands with low trans effect may decrease the activation barrier of the C-H bond cleavage.     

Nickel‐Catalyzed Cross‐Coupling of Alkyl Zinc Halides for the Formation of C(sp2)?C(sp3) Bonds: Scope and Mechanism

Optimal conditions for a general Ni‐catalysed Negishi cross‐coupling of alkyl zinc halides with aryl, heteroaryl and alkenyl halides have been determined. These conditions allow the reaction to take place smoothly, with low catalyst loading, and in the presence of a wide variety of functional groups to afford products in good yields at room temperature. DFT studies on the mechanism support the occurrence of a catalytic cycle involving transmetalation of the alkyl zinc halide to Ni^I followed by oxidative addition of the haloarene and C? C reductive elimination.     

Mechanism of dioxygen activation in 2-oxoglutarate-dependent enzymes: a hybrid DFT study

The reaction mechanism for dioxygen activation in 2-oxoglutarate-dependent enzymes has been studied by means of hybrid density functional theory. The results reported here support a mechanism in which all chemical transformations take place on a quintet potential-energy surface. More specifically, the activated dioxygen species attacks the carbonyl group of the co-substrate producing the Fe(II)-persuccinate-CO(2) complex, which readily releases the carbon dioxide molecule. The step in which the Fe(II)-peracid-CO(2) complex is formed is found to be rate-limiting and irreversible. Subsequent heterolysis of the Obond;O bond in the Fe(II)-persuccinate complex proceeds in two one-electron steps and produces the high-valent iron-oxo species Fe(IV)dbond;O, which is most likely to be responsible for oxidative reactions catalyzed by 2-oxoglutarate-dependent enzymes. The concerted pathway for simultaneous Obond;O and Cbond;C bond cleavage on the septet potential-energy surface is found to be less favorable. The relative stability of different forms of the active iron-oxo species is assessed, and the quintet five-coordinate complex is found to be most stable.     

Cover Picture: Palladium‐Catalyzed Carbon–Carbon Bond Formation and Cleavage of Organo(hydro)fullerenes (Chem. Eur. J. 19/2009)

An unexpected C? H bond dimerization reaction and C? C bond‐cleavage reaction in organo(hydro)fullerenes have been discovered. In their Communication on page 4760 ff. , K. Itami and M. Nambo describe the use of Pd catalysts for a number of interesting reactions of such fullerenes.

     

CN and CC Bond Formations in the Thermal Reactions of "Bare" Ni(NH(2) )(+) with C(2) H(4) : Mechanistic Insight on the Metal-Mediated Hydroamination of an Unactivated Olefin

Strike! While pure ammonia is out of luck, Ni(NH(2) )(+) gets one strike after another at the "ethylene bowling championship". In fact, Ni(NH(2) )(+) is so effective that no pin, not even at the neighboring lane, is safe from it.     

Aldehyde‐Assisted Hydrogen Transfer during the Formation of Hydride–Iridafurans from Alkynes and Aldehydes

The bis(ethylene) Ir^I complex [TpIr(C₂H₄)₂] ( 1 ; Tp=hydrotris(3,5‐dimethylpyrazolyl)borate) reacts with two equivalents of aromatic or aliphatic aldehydes in the presence of one equivalent of dimethyl acetylenedicarboxylate (DMAD) with ultimate formation of hydride iridafurans of the formula [TpIr(H){C(R¹)?C(R²)C(R³)O }] (R¹=R²=CO₂Me; R³=alkyl, aryl; 3 ). Several intermediates have been observed in the course of the reaction. It is proposed that the key step of metallacycle formation is a C? C coupling process in the undetected Ir^I species [TpIr{η¹‐O‐R³C(?O)H}(DMAD)] ( A ) to give the trigonal‐bipyramidal 16 e^? Ir^III intermediates [TpIr{C(CO₂Me)?C(CO₂Me)C(R³)(H)O }] ( C ), which have been trapped by NCMe to afford the adducts 11 (R³=Ar). If a second aldehyde acts as the trapping reagent for these species, this ligand acts as a shuttle in transfering a hydrogen atom from the γ‐ to the α‐carbon atom of the iridacycle through the formation of an alkoxide group. Methyl propiolate (MP) can be used instead of DMAD to regioselectively afford the related iridafurans. These reactions have also been studied by DFT calculations.     

A comprehensive theoretical study on the reactions of Sc+ with CnH2n+2 (n=1-3): structure,mechanism, and potential-energy surface

The reactions of Sc(+)((3)D) with methane, ethane, and propane in the gas phase were studied theoretically by density functional theory. The potential energy surfaces corresponding to [Sc, C(n), H(2n+2)](+) (n=1-3) were examined in detail at the B3LYP/6-311++G(3df, 3pd)//B3LYP/6-311+G(d,p) level of theory. The performance of this theoretical method was calibrated with respect to the available thermochemical data. Calculations indicated that the reactions of Sc(+) with alkanes are multichannel processes which involve two general mechanisms: an addition-elimination mechanism, which is in good agreement with the general mechanism proposed from earlier experiments, and a concerted mechanism, which is presented for the first time in this work. The addition-elimination reactions are favorable at low energy, and the concerted reactions could be alternative pathways at high energy. In most cases, the energetic bottleneck in the addition-elimination mechanism is the initial C--C or C--H activation. The loss of CH(4) and/or C(2)H(6) from Sc(+)+C(n)H(2n+2) (n=2, 3) can proceed along both the initial C--C activation branch and the Cbond;H activation branch. The loss of H(2) from Sc(+)+C(n)H(2n+2) (n=2, 3) can proceed not only by 1,2-H(2) and/or 1,3-H(2) elimination, but also by 1,1-H(2) elimination. The reactivity of Sc(+) with alkanes is compared with those reported earlier for the reactions of the late first-row transition-metal ions with alkanes.     

Palladium‐Catalyzed Carbon–Carbon Bond Formation and Cleavage of Organo(hydro)fullerenes

Palladium can tailor fullerenes : Palladium catalysts enable a number of C? H bond transformations of organo(hydro)fullerene. In addition to anticipated coupling reactions (C? H bond allylation and arylation), an unexpected new C? H bond dimerization reaction and C? C bond‐cleavage reaction were also uncovered.