Boosting Effect of Sterically Protected Glucosyl Substituents in Formic Acid Dehydrogenation by Iridium(III) 2-Pyridineamidate Catalysts.

[Cp*Ir(R-pica)Cl] (Cp*=pentamethylcyclopentadienyl anion, pica=2-picolineamidate) complexes bearing carbohydrate substituents on the amide nitrogen atom (R=methyl-ß-D-gluco-pyranosid-2-yl, 1; methyl-3,4,6-tri-O-acetyl-ß-D-glucopyranosid-2-yl, 2) were tested as catalysts for formic acid dehydrogenation in water. TOFMAX values over 12000 h-1 and 50000 h-1 were achieved at 333 K for 1 and 2, respectively, with TON values over 35000 for both catalysts. Comparison with the simpler cyclohexyl-substituted analogue (3) indicated that glucosyl-based complexes are much better performing under the same experimental conditions (TOFMAX=5144 h-1, TON=5000 at pH 2.5 for 3) owing to a lower tendency to isomerize to the less active k2-N,O isomer upon protonation. The 5-fold increase in TOFMAX observed for 2 with respect to 1 is reasonably due to an optimal steric protection by the acetyl substituent, which may prevent unproductive inner-sphere reactivity. These results showcase a powerful strategy for the inhibition of the common deactivation pathways of [Cp*Ir(R-pica)X] catalysts for FA dehydrogenation, paving the way for the development of better performing hydrogen storage systems.

A Broadened Class of Donor-Acceptor Stacked Macrometallacyclic Adducts of Different Coinage Metals.

A yet-outstanding supramolecular chemistry challenge is isolation of novel varieties of stacked complexes with finely-tuned donor-acceptor bonding and optoelectronic properties, as herein reported for binary adducts comprising two different cyclic trinuclear complexes (CTC@CTC'). Most previous attempts focused only on 1-2 factors among metal/ligand/substituent combinations, resulting in heterobimetallic complexes. Instead, here we show that, when all 3 factors are carefully considered, a broadened variety of CTC@CTC' stacked pairs with intuitively-enhanced intertrimer coordinate-covalent bonding strength and ligand-ligand/metal-ligand dispersion are attained (dM-M' 2.868(2) Å; ΔE>50 kcal/mol, an order of magnitude higher than aurophilic/metallophilic interactions). Significantly, CTC@CTC' pairs remain intact/strongly-bound even in solution (Keq 4.67×105 L/mol via NMR/UV-vis titrations), and the gas phase (mass spectrometry revealing molecular peaks for the entire CTC@CTC' units in sublimed samples), rather than simple co-crystal formation. Photo-/electro-luminescence studies unravel metal-centered phosphorescence useful for novel all metal-organic light-emitting diodes (MOLEDs) optoelectronic device concepts. This work manifests systematic design of supramolecular bonding and multi-faceted spectral properties of pure metal-organic macrometallacyclic donor/acceptor (inorganic/inorganic) stacks with remarkably-rich optoelectronic properties akin to well-established organic/organic and organic/inorganic analogues.

Solution Structure and Dynamics of Hf-Al and Hf-Zn Heterobimetallic Adducts Mimicking Relevant Intermediates in Chain Transfer Reactions.

Cationic cyclometalated hafnocenes [CpPrCpCH2CH2CH2Hf][B(C6F5)4] (4Pr) and [CpiBuCpCH2CH(Me)CH2Hf][B(C6F5)4] (4aiBu and 4biBu) were synthesized from the corresponding [(CpPr)2HfMe][B(C6F5)4] (1Pr) and [(CpiBu)2HfMe][B(C6F5)4] (1iBu) complexes via C-H activation. 4aiBu, 4biBu, and 4Pr, mimicking a propagating M-polymeryl species (M = transition metal) with or without a ß-methyl branch on the metalated chains, serve to investigate whether and how the nature of the last inserted olefin molecules changes the structure, stability, and reactivity of the corresponding heterobimetallic complexes, formed in the presence of aluminum- or zinc-alkyl chain transfer agents (CTAs), which are considered relevant intermediates in coordinative chain transfer polymerization (CCTP) and chain shuttling polymerization (CSP) technologies. NMR and DFT data indicate no major structural difference between the resulting heterobridged complexes, all characterized by the presence of multiple α-agostic interactions. On the contrary, thermodynamic and kinetic investigations, concerning the reversible formation and breaking of heterobimetallic adducts, demonstrate that isomer 4aiBu, in which the ß-Me is oriented away from the reactive coordination site on Hf, but not 4biBu, having the ß-Me pointing in the opposite direction, is capable of reacting with CTAs. Quantification of kinetic rate constants highlights that the formation process is rate limiting and that the nature of the last inserted α-olefin unit modulates transalkylation kinetics. The reaction of 4aiBu, 4biBu, and 4Pr with diisobutylaluminum hydride (DiBAlH) allows the interception and characterization of new heterobinuclear and heterotrinuclear species, featuring both hydride and alkyl bridging moieties, which represent structural models of elusive intermediates in CCTP and CSP processes, capturing the instant when an alkyl chain has just transferred from a transition metal to a main group metal, while the two metals remain engaged in a single heterobimetallic intermediate.

Harnessing the electronic structure of active metals to lower the overpotential of the electrocatalytic oxygen evolution reaction.

Despite substantial advancements in the field of the electrocatalytic oxygen evolution reaction (OER), the efficiency of earth-abundant electrocatalysts remains far from ideal. The difficulty stems from the complex nature of the catalytic system, which limits our fundamental understanding of the process and thus the possibility of a rational improvement of performance. Herein, we shed light on the role played by the tunable 3d configuration of the metal centers in determining the OER catalytic activity by combining electrochemical and spectroscopic measurements with an experimentally validated computational protocol. One-dimensional coordination polymers based on Fe, Co and Ni held together by an oxonato linker were selected as a case study because of their well-defined electronic and geometric structure in the active site, which can be straightforwardly correlated with their catalytic activity. Novel heterobimetallic coordination polymers were also considered, in order to shed light on the cooperativity effects of different metals. Our results demonstrate the fundamental importance of electronic structure effects such as metal spin and oxidation state evolutions along the reaction profile to modulate ligand binding energies and increase catalyst efficiency. We demonstrated that these effects could in principle be exploited to reduce the overpotential of the electrocatalytic OER below its theoretical limit, and we provide basic principles for the development of coordination polymers with a tailored electronic structure and activity.

Cocatalyst effects in Hf-catalysed olefin polymerization: taking well-defined Al-alkyl borate salts into account.

Hafnium catalysts for olefin polymerization are often very sensitive to the nature of cocatalysts, especially if they contain "free" aluminium trialkyls. Herein, cocatalyst effects in Hf-catalysed propene polymerization are examined for four Hf catalysts belonging to the family of CS-symmetric (Hf-CS-Met) and C2-symmetric (Hf-C2-Met) metallocenes, as well as of octahedral (Hf-OOOO) and pentacoordinated (Hf-PyAm) "post-metallocenes". The performance of the recently developed {[iBu2(PhNMe2)Al]2(µ-H)}+[B(C6F5)4]- (AlHAl) cocatalyst is compared with that of established systems like methylalumoxane, phenol-modified methylalumoxane and trityl borate/tri-iso-butylaluminium. The worst catalytic performance is observed with MAO. Conversely, the best cocatalyst varies depending on the Hf catalyst used and the performance indicator of interest, highlighting the complexity and importance of selecting the right precatalyst/cocatalyst combination. AlHAl proved to be a suitable system for all catalysts tested and, in some cases, it provides the best performance in terms of productivity (e.g. with hafnocenes). Furthermore, it generally leads to high molecular weight polymers, also with catalysts enabling easy chain transfer to Al like Hf-PyAm. This suggests that AlHAl has a low tendency to form heterodinuclear adducts with the cationic active species, therefore preventing the formation of dormant sites and/or termination events by chain transfer to Al.

Octahedral Zirconium Salan Catalysts for Olefin Polymerization: Substituent and Solvent Effects on Structure and Dynamics.

Group 4 metal-Salan olefin polymerization catalysts typically have relatively low activity, being slowed down by a pre-equilibrium favoring a non-polymerization active resting state identified as a mer-mer isomer (MM); formation of the polymerization active fac-fac species (FF) requires isomerization. We now show that the chemistry is more subtle than previously realized. Salan variations bearing large, flat substituents can achieve very high activity, and we ascribe this to the stabilization of the FF isomer, which becomes lower in energy than MM. Detailed in situ NMR studies of a fast (o-anthracenyl) and a slow (o-tBu) Salan precursors, suitably activated, indicate that preferred isomers in solution are different: the fast catalyst prefers FF while the slow catalyst prefers a highly distorted MM geometry. Crystal structures of the activated o-anthracenyl substituted complex with a moderately (chlorobenzene) and, more importantly, a weakly coordinating solvent (toluene) in the first coordination sphere emphasize that the active FF isomer is preferred, at least for the benzyl species. Site epimerization (SE) barriers for the fast catalyst (ΔS > 0, dissociative) and the slow catalyst (ΔS < 0, associative) in toluene corroborate the solvent role. Diagnostic NMe 13C chemical shift differences allow unambiguous detection of FF or MM geometries for seven activated catalysts in different solvents, highlighting the role of solvent coordination strength and bulkiness of the ortho-substituent on the isomer equilibrium. For the first time, active polymeryl species of Zr-Salan catalysts were speciated. The slow catalyst is effectively trapped in the inactive MM state, as previously suggested. Direct observation of fast catalysts is hampered by their high reactivity, but the product of the first 1-hexene insertion maintains its FF geometry.

A Hydrocarbon Soluble, Molecular and "Complete" Al-Cocatalyst for High Temperature Olefin Polymerization.

The dinuclear aluminum salt {[iBu2(DMA)Al]2(µ-H)}+[B(C6F5)4]- (AlHAl; DMA = N,N-dimethylaniline) is the prototype of a new class of molecular cocatalysts for catalytic olefin polymerization, its modular nature offering easy avenues for tailoring the activator to specific needs. We report here, as proof of concept, a first variant (s-AlHAl) bearing p-hexadecyl-N,N-dimethylaniline (DMAC16) units, which enhances solubility in aliphatic hydrocarbons. The novel s-AlHAl was used successfully as an activator/scavenger in ethylene/1-hexene copolymerization in a high-temperature solution process.

Tweaking the bridge in metallocene Zr(IV)/W(IV) bimetallic hydrides.

Zirconocene cations react with Cp2WH2 affording the bimetallic [Cp2Zr(µ-H)(µ-η1:η5-C5H4)WHCp]+ bridging hydride 1 (Cp = cyclopentadienyl anion, C5H5-) via σ-bond metathesis. Complex 1 features an atypical out of plane Zr(µ-H)W moiety, where no intermetallic interaction is involved, and a fluxional core. Coordination geometry and bond distances of the bridging hydride interaction can be modulated upon reaction with Lewis bases and unsaturated substrates. PMe3, P(p-tol)3, 3,5-dimethylpyridine and THF bind to 1 and shift the hydride bridge on the coordination plane of Zr. Insertion of olefins and alkynes into the Zr-C bond of 1 leads instead to alkyl and vinyl species where the Zr and W coordination planes are perpendicular to each other. Such alterations of the Zr(µ-H)W arrangement are reflected in the average 1H NMR chemical shift values of the hydride, which correlate linearly with computed Zr-H distances. Reactivity experiments with H2 showed that the bridging hydride interaction prevents bimetallic cooperativity and that σ-bond metathesis between Zr-C and H-H bonds is the preferred pathway for all the investigated complexes.

Efficient Hydrogenation of N-Heterocycles Catalyzed by NNP-Manganese(I) Pincer Complexes at Ambient Temperature.

Manganese-catalyzed hydrogenation reactions have aroused widespread interest in recent years. Among the catalytic systems described, especially PNP- and NNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, ketones, nitriles, aldimines and esters. Furthermore, NNP-Mn pincer compounds are efficient catalysts for the hydrogenolysis of less reactive amides, ureas, carbonates, and carbamates. Herein, the synthesis and application of specific imidazolylaminophosphine ligands and the corresponding Mn pincer complexes are described. These new catalysts have been characterized and studied by a combination of experimental and theoretical investigations, and their catalytic activities have been tested in several hydrogenation reactions with good to excellent performance. Especially, the reduction of N-heterocycles can be performed under very mild conditions.

Single-Site Iridium Picolinamide Catalyst Immobilized onto Silica for the Hydrogenation of CO2 and the Dehydrogenation of Formic Acid.

The development of an efficient heterogeneous catalyst for storing H2 into CO2 and releasing it from the produced formic acid, when needed, is a crucial target for overcoming some intrinsic criticalities of green hydrogen exploitation, such as high flammability, low density, and handling. Herein, we report an efficient heterogeneous catalyst for both reactions prepared by immobilizing a molecular iridium organometallic catalyst onto a high-surface mesoporous silica, through a sol-gel methodology. The presence of tailored single-metal catalytic sites, derived by a suitable choice of ligands with desired steric and electronic characteristics, in combination with optimized support features, makes the immobilized catalyst highly active. Furthermore, the information derived from multinuclear DNP-enhanced NMR spectroscopy, elemental analysis, and Ir L3-edge XAS indicates the formation of cationic iridium sites. It is quite remarkable to note that the immobilized catalyst shows essentially the same catalytic activity as its molecular analogue in the hydrogenation of CO2. In the reverse reaction of HCOOH dehydrogenation, it is approximately twice less active but has no induction period.

Efficient enantioresolution of aromatic α-hydroxy acids with Cinchona alkaloid-based zwitterionic stationary phases and volatile polar-ionic eluents.

Single enantiomers of mandelic acid (1), 3-phenyllactic acid (2), and 3-(4-hydroxyphenyl)lactic acid (3) are the subject of many fields of investigation, spanning from the pharmaceutical synthesis to that of biocompatible and biodegradable polymers, while passing from the interest towards their antimicrobial activity to their role as biomarkers of particular pathological conditions or occupational exposures to specific xenobiotics. All above mentioned issues justify the need for accurate analytical methods enabling the correct determination of the individual enantiomers. So far, all the developed liquid chromatography (LC) methods were not or hardly compatible with mass spectrometry (MS) detection. In this paper, a commercially available Cinchona-alkaloid derivative zwitterionic chiral stationary phase [that is, the CHIRALPAK® ZWIX(-)] was successfully used to optimize the enantioresolution of compounds 1-3 under polar-ionic (PI) conditions with a mobile phase consisting of an acetonitrile/methanol 95/5 (v/v) mixture with 80 mM formic acid. With the optimized conditions, enantioseparation and enantioresolution values up to 1.46 and 4.41, respectively, were obtained. In order to assess the applicability of the optimized enantioselective chromatography conditions in real-life scenarios and on MS-based systems, a proof-of-concept application was efficiently carried out by analysing dry urine spot samples spiked with 1 by means of a LC-MS system. The (S)<(R) enantiomer elution order (EEO) was established for compounds 1 and 2 by analysing a pure enantiomeric standard of known configuration. This was not possible for 3 because not commercially available. For this compound, the same EEO was identified applying a procedure based on ab initio time-dependent density-functional theory simulations coupled to electronic circular dichroism analyses. Moreover, a molecular dynamics simulation unveiled the role of the phenolic OH in compound 3 in the retention mechanism.

Understanding the Deactivation Pathways of Iridium(III) Pyridine-Carboxiamide Catalysts for Formic Acid Dehydrogenation.

The degradation pathways of highly active [Cp*Ir(κ2 -N,N-R-pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO3 ), 2 undergoes partial protonation of the amide moiety, inducing rapid κ2 -N,N to κ2 -N,O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ2 -N,N key intermediate of FA dehydrogenation (INH ), bearing a N-protonated pica, can easily transform into the κ2 -N,O analogue (INH2 ; ΔG≠ ≈11 kcal mol-1 , ΔG ≈-5 kcal mol-1 ). Intramolecular hydrogen liberation from INH2 is predicted to be rather prohibitive (ΔG≠ ≈26 kcal mol-1 , ΔG≈23 kcal mol-1 ), indicating that FA dehydrogenation should involve mostly κ2 -N,N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*-complexes with a pyridine-amine ligand. This likely derived from hydrogenation of the pyridine-carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c. DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible.

Iridium-Doped Nanosized Zn-Al Layered Double Hydroxides as Efficient Water Oxidation Catalysts.

Layered double hydroxides (LDHs) are an ideal platform to host catalytic metal centers for water oxidation (WO) owing to the high accessibility of water to the interlayer region, which makes all centers potentially reachable and activated. Herein, we report the syntheses of three iridium-doped zinc-aluminum LDHs (Ir-LDHs) nanomaterials (1-3, with about 80 nm of planar size and a thickness of 8 nm as derived by field emission scanning electron microscopy and powder X-ray diffraction studies, respectively), carried out in the confined aqueous environment of reverse micelles, through a very simple and versatile procedure. These materials exhibit excellent catalytic performances in WO driven by NaIO4 at neutral pH and 25 °C, with an iridium content as low as 0.5 mol % (∼0.8 wt %), leading to quantitative oxygen yields (based on utilized NaIO4, turnover number up to ∼10,000). Nanomaterials 1-3 display the highest ever reported turnover frequency values (up to 402 min-1) for any heterogeneous and heterogenized catalyst, comparable only to those of the most efficient molecular iridium catalysts, tested under similar reaction conditions. The boost in activity can be traced to the increased surface area and pore volume (>5 times and 1 order of magnitude, respectively, higher than those of micrometric materials of size 0.3-1 µm) estimated for the nanosized particles, which guarantee higher noble metal accessibility. X-ray absorption spectroscopy (XAS) studies suggest that 1-3 nanomaterials, as-prepared and after catalysis, contain a mixture of isolated, single octahedral Ir(III) sites, with no evidence of Ir-Ir scattering from second-nearest neighbors, excluding the presence of IrO2 nanoparticles. The combination of the results obtained from XAS, elemental analysis, and ionic chromatography strongly suggests that iridium is embedded in the brucite-like structure of LDHs, having four hydroxyls and two chlorides as first neighbors. These results demonstrate that nanometric LDHs can be successfully exploited to engineer efficient WOCs, minimizing the amount of iridium used, consistent with the principle of the noble-metal atom economy.

The Influence of the Ligand in the Iridium Mediated Electrocatalyic Water Oxidation.

Electrochemical water oxidation is the bottleneck of electrolyzers as even the best catalysts, iridium and ruthenium oxides, have to operate at significant overpotentials. Previously, the position of a hydroxyl on a series of hydroxylpicolinate ligands was found to significantly influence the activity of molecular iridium catalysts in sacrificial oxidant driven water oxidation. In this study, these catalysts were tested under electrochemical conditions and benchmarked to several other known molecular iridium catalysts under the exact same conditions. This allowed us to compare these catalysts directly and observe whether structure-activity relationships would prevail under electrochemical conditions. Using both electrochemical quartz crystal microbalance experiments and X-ray photoelectron spectroscopy, we found that all studied iridium complexes form an iridium deposit on the electrode with binding energies ranging from 62.4 to 62.7 eV for the major Ir 4f7/2 species. These do not match the binding energies found for the parent complexes, which have a broader binding energy range from 61.7 to 62.7 eV and show a clear relationship to the electronegativity induced by the ligands. Moreover, all catalysts performed the electrochemical water oxidation in the same order of magnitude as the maximum currents ranged from 0.2 to 0.6 mA cm-2 once more without clear structure-activity relationships. In addition, by employing 1H NMR spectroscopy we found evidence for Cp* breakdown products such as acetate. Electrodeposited iridium oxide from ligand free [Ir(OH)6]2- or a colloidal iridium oxide nanoparticles solution produces currents almost 2 orders of magnitude higher with a maximum current of 11 mA cm-2. Also, this deposited material contains, apart from an Ir 4f7/2 species at 62.4 eV, an Ir species at 63.6 eV, which is not observed for any deposit formed by the molecular complexes. Thus, the electrodeposited material of the complexes cannot be directly linked to bulk iridium oxide. Small IrOx clusters containing few Ir atoms with partially incorporated ligand residues are the most likely option for the catalytically active electrodeposit. Our results emphasize that structure-activity relationships obtained with sacrificial oxidants do not necessarily translate to electrochemical conditions. Furthermore, other factors, such as electrodeposition and catalyst degradation, play a major role in the electrochemically driven water oxidation and should thus be considered when optimizing molecular catalysts.

Reactivity Trends of Lewis Acidic Sites in Methylaluminoxane and Some of Its Modifications.

The established model cluster (AlOMe)16(AlMe3)6 for methylaluminoxane (MAO) cocatalyst has been studied by density functional theory, aiming to rationalize the different behaviors of unmodified MAO and TMA-depleted MAO/BHT (TMA = trimethylaluminum; BHT = 2,6-di-tert-butyl-4-methylphenol), highlighted in previous experimental studies. The tendency of the three model Lewis acidic sites A-C to release neutral Al fragments (i.e., AlMe2R; R = Me or bht) or transient aluminum cations (i.e., [AlMeR]+) has been investigated both in the absence and in the presence of neutral N-donors. Sites C are most likely responsible for the activation capabilities of TMA-rich MAO, but TMA depletion destabilizes them, possibly inducing structural rearrangements. The remaining sites A and B, albeit of lower Lewis acidity, should be still able to release cationic Al fragments when TMA-depleted modified MAOs are treated with N-donors (e.g. [AlMe(bht)]+ from MAO/BHT). These findings provide tentative interpretations for earlier observations of donor-dependent ionization tendencies of MAO and MAO/BHT and how TMA depleted MAOs can still be potent activators.

Interception of Elusive Cationic Hf-Al and Hf-Zn Heterobimetallic Adducts with Mixed Alkyl Bridges Featuring Multiple Agostic Interactions.

Invited for the cover of this issue is the group of Cristiano Zuccaccia at the Università degli Studi di Perugia. The image depicts a relation of the nuances of chemical bonding to the diverse ways that animals "bind" to their natural surroundings. Read the full text of the article at 10.1002/chem.201905699.

H2 activation by zirconaziridinium ions: σ-bond metathesis versus frustrated Lewis pair reactivity.

Zirconaziridinium ions [Cp2Zr(η2-CH2NR2)]+ can potentially activate H2 by two routes: σ-bond metathesis or FLP reactivity. We show here that Zr-C hydrogenolysis by σ-bond metathesis precedes and enables subsequent heterolytic H2 cleavage through FLP pathways. DFT calculations show the involvement of transition states with approximately linear NHH and bent ZrHH arrangements without any direct Zr-amine interaction.

Interception of Elusive Cationic Hf-Al and Hf-Zn Heterobimetallic Adducts with Mixed Alkyl Bridges Featuring Multiple Agostic Interactions.

Heterobimetallic complexes with inequivalent bridging alkyl chains are very often invoked as key intermediates in many catalytic processes, yet their interception and structural characterization are lacking. Such complexes have been prepared from reactions of the cationic cyclometalated hafnocene [CpPr Cp CH 2 CH 2 CH 2 Hf][B(C6 F5 )4 ] (1) with main group metal alkyls to afford the corresponding hetero-bridged cationic products, [CpPr Cp CH 2 CH 2 ( µ - CH 2 ) Hf(µ-R)E(R)n ][B(C6 F5 )4 ] (E=Al or Zn; R=Me, Et, or iBu). NMR and DFT studies demonstrate that both bridging alkyls establish agostic interactions with Hf, which are appreciably stronger for ethyl rather than methyl groups. Hf-Al and Hf-Zn distances are surprisingly short and only slightly longer than computed Hf-Al or Hf-Zn single bond lengths (2.80 Å). Finally, a reaction of [CpPr Cp CH 2 CH 2 ( µ - CH 2 ) Hf(µ-Me)Zn(Me)][B(C6 F5 )4 ] with excess ZnMe2 yields an unprecedented heterotrimetallic species, [(CpPr )2 Hf(µ-Me)(ZnMe)(µ3 -CH2 )ZnMe][B(C6 F5 )4 ], the detailed structure of which is elucidated by a combination of NMR spectroscopic methods and molecular calculations.

Ir- and Ru-doped layered double hydroxides as affordable heterogeneous catalysts for electrochemical water oxidation.

Three M-doped LDHs (M = noble metal active site, LDH = layered double hydroxides; Ir-1, Ir-ZnAl; Ru, Ru-ZnAl; Ir-2, Ir-MgAl), containing small amounts of M (ca. 2 mol% and even <1 mol% for Ru and Ir, respectively), were prepared by following simple and established synthetic procedures. Their characterization indicates that M atoms are effectively incorporated into the brucite-like layers of LDH, without phase segregation. The resulting materials catalyse electrochemical water oxidation (WO), when immobilized in carbon paste electrodes, with performances that exceed those of the benchmark system IrO2, as probed by linear sweep voltammetry (LSV). Some of these catalysts undergo continuous activation upon chronoamperometric and chronopotentiometric treatments over several hours. The crystalline structure of all of them is preserved during electrocatalytic experiments, and no significant leaching of noble metal in solution is detected. The results herein reported highlight the remarkable potential of these doped M-LDHs and confirm that dispersing Ir and Ru centers in layered and cheap inorganic materials results in easily accessible metal centers, providing highly active catalysts, while minimizing the utilization of noble metals.

Molecular and heterogenized dinuclear Ir-Cp* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands.

The development of efficient water oxidation catalysts (WOCs) is of key importance in order to drive sustainable reductive processes aimed at producing renewable fuels. Herein, two novel dinuclear complexes, [(Cp*Ir)2(µ-κ3-O,N,O-H4-EDTMP)] (Ir-H4-EDTMP, H4-EDTMP4- = ethylenediamine tetra(methylene phosphonate)) and [(Cp*Ir)2(µ-κ3-O,N,O-EDTA)] (Ir-EDTA, EDTA4- = ethylenediaminetetraacetate), were synthesized and completely characterized in solution, by multinuclear and multidimensional NMR spectroscopy, and in the solid state, by single crystal X-Ray diffraction. They were supported onto rutile TiO2 nanocrystals obtaining Ir-H4-EDTMP@TiO2 and Ir-EDTA@TiO2 hybrid materials. Both molecular complexes and hybrid materials were found to be efficient catalysts for WO driven by NaIO4, providing almost quantitative yields, and TON values only limited by the amount of NaIO4 used. As for the molecular catalysts, Ir-H4-EDTMP (TOF up to 184 min-1) exhibited much higher activity than Ir-EDTA (TOF up to 19 min-1), likely owing to the higher propensity of the former to generate a coordination vacancy through the dissociation of a Ir-OP bond (2.123 Å, significantly longer than Ir-OC, 2.0913 Å), which is a necessary step to activate these saturated complexes. Ir-H4-EDTMP@TiO2 (up to 33 min-1) and Ir-EDTA@TiO2 (up to 41 min-1) hybrid materials showed similar activity that was only marginally reduced in the second and third catalytic runs carried out after having separated the supernatant, which did not show any sign of activity, instead. The observed TOF values for hybrid materials are higher than those reported for analogous systems deriving from heterogenized mononuclear complexes. This suggests that supporting dinuclear molecular precursors could be a successful strategy to obtain efficient heterogenized water oxidation catalysts.