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A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from the bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H 2 followed by O 2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate-determining. Electronic-structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from one involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H 2 and, alternatively, with D 2 on the cluster incorporating the dioxygen ligands and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H 2 with D 2 to give HD. We posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.

Although oxygen is a common ligand in supported metal catalysts, its coordination has been challenging to elucidate. We now characterize a diiridium complex that has been previously shown by X-ray diffraction crystallography to incorporate a μ-η 1 :η 1 -peroxo ligand. We observe markedly enhanced intensity at 788 cm -1 in the Raman spectrum of this complex, which is a consequence of bonding of the peroxo ligand but does not shift upon 18 O labeling. Electronic structure calculations at the density functional theory level suggest that this increase in Raman intensity results from bands associated with rocking of CH 2 substituents directly attached to P(Ph) 2 groups coupling with the O-O band. These results provide part of the foundation for understanding oxygen ligands on a silica-supported tetrairidium carbonyl cluster stabilized with bulky electron-donating phosphine ligands [ p - tert -butyl-calix[4]arene(OPr) 3 (OCH 2 PPh 2 ) (Ph = phenyl; Pr = propyl)]. Reaction of the cluster with O 2 also led to the growing in of a Raman band at 788 cm -1 , similar to that in the diiridium complex and also assigned to the bonding of a bridging peroxo ligand. Infrared spectra recorded as the supported cluster reacted in sequential exposures to (i) H 2 , (ii) O 2 , (iii) H 2 , and (iv) CO indicate that two bridging peroxo ligands were bonded irreversibly per tetrairidium cluster, replacing bridging carbonyl ligands without altering either the cluster frame or the phosphine ligands. X-ray absorption near edge and infrared spectra include isosbestic points signifying a stoichiometrically simple reaction of the cluster with O 2 , and mass spectra of the effluent gas show that CO 2 formed by oxidation of one terminal CO ligand per cluster as H 2 (and not H 2 O) formed, evidence that hydride ligands had been present on the cluster following treatment (i). The understanding of how O 2 reacts with the metal polyhedron provides a foundation for understanding of how oxidation catalysis may proceed on the surfaces of noble metals.

The effect of dynamic reorganization and confinement of isolated Ti IV catalytic centers supported on silicates is investigated for olefin epoxidation. Active sites consist of grafted single-site calix[4]arene-Ti IV centers or their calcined counterparts. Their location is synthetically controlled to be either unconfined at terminal T-atom positions (denoted as type-(i)) or within confining 12-MR pockets (denoted as type-(ii); diameter ∼7 Å, volume ∼185 Å 3 ) composed of hemispherical cavities on the external surface of zeotypes with *-SVY topology. Electronic structure calculations (density functional theory) indicate that active sites consist of cooperative assemblies of Ti IV centers and silanols. When active sites are located at unconfined type-(i) environments, the rate constants for cyclohexene epoxidation (323 K, 0.05 mM Ti IV , 160 mM cyclohexene, 24 mM tert-butyl hydroperoxide) are 9 ± 2 M -2 s -1 ; whereas within confining type-(ii) 12-MR pockets, there is a ∼5-fold enhancement to 48 ± 8 M -2 s -1 . When a mixture of both environments is initially present in the catalyst resting state, the rate constants reflect confining environments exclusively (40 ± 11 M -2 s -1 ), indicating that dynamic reorganization processes lead to the preferential location of active sites within 12-MR pockets. While activation enthalpies are Δ H ‡ app = 43 ± 1 kJ mol -1 irrespective of active site location, confining environments exhibit diminished entropic barriers (Δ S ‡ app = -68 J mol -1 K -1 for unconfined type-(i) vs -56 J mol -1 K -1 for confining type-(ii)), indicating that confinement leads to more facile association of reactants at active sites to form transition state structures (volume ∼ 225 Å 3 ). These results open new opportunities for controlling reactivity on surfaces through partial confinement on shallow external-surface pockets, which are accessible to molecules that are too bulky to benefit from traditional confinement within micropores.

Although essentially molecular noble metal species provide active sites and highly tunable platforms for the design of supported catalysts, the susceptibility of the metals to reduction and aggregation and the consequent loss of catalytic activity and selectivity limit opportunities for their application. Here, we demonstrate a new construct to stabilize supported molecular noble-metal catalysts, taking advantage of sterically bulky ligands on the metal that serve as surrogate supports and isolate the active sites under conditions involving steady-state catalytic turnover in a reducing environment. The result is demonstrated with an iridium pair-site catalyst incorporating P-bridging calix[4]arene ligands dispersed on siliceous supports, chosen as prototypes because they offer weakly interacting surfaces on which metal aggregation is prone to occur. This catalyst was used for the hydrogenation of ethylene in a flow reactor. Atomic-resolution imaging of the Ir centers and spectra of the catalyst before and after use show that the metals resisted aggregation and deactivation, remaining atomically dispersed and accessible for catalysis. This strategy thus allows the stabilization of the catalysts even when they are weakly anchored to supports.

The separation of aromatic contaminants from sugar-aromatic aqueous mixtures is required in second-generation biorefineries because aromatic compounds deactivate (bio)catalysts typically involved in upgrading lignocellulosic biomass to fuels and chemicals. This separation remains challenging, however, because of the degree of molecular recognition needed to sequester dilute aromatic impurities from concentrated sugar streams. Herein, we demonstrate that hydrophobic cavities of p- tert-butylcalix[4]arene macrocycles grafted on amorphous silica (calix/SiO 2 ) perform this separation selectively and efficiently by acting as selective molecular hosts that adsorb aromatic compounds (5-hydroxymethylfurfural, vanillin, and vanillic acid) while excluding monomeric sugar (glucose chosen as a prototypical model) in aqueous mixtures. By comparing calix/SiO 2 to a range of organically modified SiO 2 surfaces and other porous adsorbents, we demonstrate that the organization of hydrophobic functional groups within discrete nests consisting of calixarene cavities is crucial for facilitating the adsorption of aromatics. Density functional theory calculations of the host-guest complex indicate that adsorption is brought about by weak dispersive (van der Waals) interactions between tert-butyl upper-rim substituents in calixarene hosts and aromatic guests. Calix/SiO 2 can be repeatedly reused, demonstrating its viability as an adsorbent within a continuous biorefining process. These calix/SiO 2 adsorbents expand the palette of materials available for selective sugar-aromatic separations, which until now have been limited to pyrene-based sites of metal-organic framework NU-1000, and demonstrate that sites consisting of relatively simple hydrophobic tert-butyl substituents organized around a hemispherical molecular cavity provide a sufficient degree of molecular recognition for performing this separation selectively.

The effect of outer-sphere environment on alkene epoxidation catalysis using an organic hydroperoxide oxidant is demonstrated for calix[4]arene-Ti IV single-sites grafted on amorphous vs crystalline delaminated zeotype (UCB-4) silicates as supports. A chelating calix[4]arene macrocyclic ligand helps enforce a constant Ti IV inner-sphere, as characterized by UV-visible and X-ray absorption spectroscopies, thus enabling the rigorous comparison of outer-sphere environments across different siliceous supports. These outer-sphere environments are characterized by solid-state 1 H NMR spectroscopy to comprise proximally organized silanols confined within 12 membered-ring cups in crystalline UCB-4, and are responsible for up to 5-fold enhancements in rates of epoxidation by Ti IV centers.