Heterolytic CH Activation and Catalysis by an O-Donor Iridium−Hydroxo Complex

A well-defined, O-donor ligated iridium hydroxide complex is reported that is competent for benzene CH activation and long-lived catalytic H/D exchange between benzene and water. An inverse dependence of the H/D exchange rate on added pyridine, a kinetic isotope effect (KIE) of 2.65 ± 0.56 for CH activation with 1,3,5-trideuteriobenzene, a KIE of 1.07 ± 0.24 with C_6H_6/C_6D_6, and DFT calculations are consistent with the CH activation proceeding via rate-determining benzene coordination followed by fast CH cleavage via a σ-bond-metathesis transition state

CH Activation with an O-Donor Iridium−Methoxo Complex

A thermally and air stable O-donor, iridium−methoxo complex is reported that undergoes stoichiometric, intermolecular C−H activation of benzene with co-generation of methanol and the iridium−phenyl complex

Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

We report that SeO_2 catalyzes the facile oxy-functionalization of (CO)_5Re(I)-Me^(δ−) with IO_4− to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH_3Se(VI) species. Furthermore, (CO)_3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO_2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M−R^(δ−) polarized bonds

Mechanism of efficient anti-Markovnikov olefin hydroarylation catalyzed by homogeneous Ir(III) complexes

The mechanism of the hydroarylation reaction between unactivated olefins (ethylene, propylene, and styrene) and benzene catalyzed by [(R)Ir(μ-acac-O,O,C^3)-(acac-O,O)_2]_2 and [R-Ir(acac-O,O)_2(L)] (R = acetylacetonato, CH_3, CH_2CH_3, Ph, or CH_2CH_2Ph, and L = H_2O or pyridine) Ir(III) complexes was studied by experimental methods. The system is selective for generating the anti-Markovnikov product of linear alkylarenes (61 : 39 for benzene + propylene and 98 : 2 for benzene + styrene). The reaction mechanism was found to follow a rate law with first-order dependence on benzene and catalyst, but a non-linear dependence on olefin. ^(13)C-labelling studies with CH_3^(13)CH_2-Ir-Py showed that reversible β-hydride elimination is facile, but unproductive, giving exclusively saturated alkylarene products. The migration of the ^(13)C-label from the α to β-positions was found to be slower than the C–H activation of benzene (and thus formation of ethane and Ph-d_5-Ir-Py). Kinetic analysis under steady state conditions gave a ratio of the rate constants for CH activation and β-hydride elimination (k_(CH): k_β) of 0.5. The comparable magnitude of these rates suggests a common rate determining transition state/intermediate, which has been shown previously with B3LYP density functional theory (DFT) calculations. Overall, the mechanism of hydroarylation proceeds through a series of pre-equilibrium dissociative steps involving rupture of the dinuclear species or the loss of L from Ph-Ir-L to the solvento, 16-electron species, Ph-Ir(acac-O,O)_2-Sol (where Sol refers to coordinated solvent). This species then undergoes trans to cis isomerization of the acetylacetonato ligand to yield the pseudo octahedral species cis-Ph-Ir-Sol, which is followed by olefin insertion (the regioselective and rate determining step), and then activation of the C–H bond of an incoming benzene to generate the product and regenerate the catalyst

Facile Functionalization of a Metal Carbon Bond by O-Atom Transfer

The facile conversion of M−R to M−OR that could be useful for the functionalization of electron-rich metal alkyl intermediates is shown to proceed via a Baeyer−Villiger-type pathway involving a nonredox, electrophilic, O-atom insertion in reactions with non-peroxo O-donors

Design and study of homogeneous catalysts for the selective, low temperature oxidation of hydrocarbons

The direct, low temperature conversion of hydrocarbons to functionalized products using novel, single site catalysts could lead to technological advances that redefine the landscape of the current materials and energy industries. Natural gas continues to represent a vast source of untapped hydrocarbons around the globe that has the potential to replace or augment petroleum as the raw material for materials and energy. Its abundance has garnered much interest in the scientific community as groups have focused on the catalytic conversion of its major component, methane, to functionalized products. The key requirements is to design new catalysts for the oxidative functionalization of methane that operate at lower temperatures and that also meet the basic requirements of selectivity, rate, and lifetime that characterize useful catalysts. Recent advances in the field of hydrocarbon CH activation have shown the potential for transition metal based coordination catalysts to meet these requirements. Described herein are recent advances in designing catalysts based on the CH activation reaction that address the basic requirements for practical systems with emphasis on the issues that have prevented promising reported systems from becoming commercially viable