The Still Elusive Role of Lightweight Doping in Carbon-Based Electrocatalysts for the Selective Oxygen Reduction Reaction to Hydrogen Peroxide.

The two-electron electrocatalytic oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2) is a valuable alternative to the more conventional and energy-intensive anthraquinone process. From a circularity viewpoint, metal-free catalysts constitute a sustainable alternative for the process. In particular, lightweight hetero-doped C-materials are cost-effective and easily scalable samples that replace - more and more frequently - the use of critical raw elements in the preparation of highly performing (electro)catalysts. Anyhow, their large-scale exploitation in industrial processes still suffers from technical limits of samples upscale and reproducibility other than a still moderate comprehension of their action mechanism in the process. This concept article offers a comprehensive and exhaustive "journey" through the most representative lightweight hetero-doped C-based electrocatalysts and their performance in the 2e- ORR process. It provides an interpretation of phenomena at the triple-phase interface of solid catalyst, liquid electrolyte and gaseous oxygen based on the doping-driven generation of ideal electronic microenvironments at the catalyst surface.

Rhenium Alkyne Catalysis: Sterics Control the Reactivity.

Metathesis reactions, including alkane, alkene, and alkyne metatheses, have their origins in the fundamental understanding of chemical reactions and the development of specialized catalysts. These reactions stand as transformative pillars in organic chemistry, providing efficient rearrangement of carbon-carbon bonds and enabling synthetic access to diverse and complex compounds. Their impact spans industries such as petrochemicals, pharmaceuticals, and materials science. In this work, we present a detailed mechanistic study of the Re(V) catalyzed alkyne metathesis through density functional theory calculations. Our findings are in agreement with the experimental evidence from Jia and co-workers and unveil critical factors governing catalyst performance. Our work not only enhances our understanding of alkyne metathesis but also contributes to the broader landscape of catalytic processes, facilitating the design of more efficient and selective transformations in organic synthesis.

Ab initio molecular dynamics of solvation effects and reactivity at the interface between water and ascorbic acid covered anatase TiO2 (101).

In this work, we present a detailed study of the interaction between ascorbic acid (L-asc) and anatase TiO2 (101) surface both in gas phase and in contact with water by using density functional theory and ab initio molecular dynamics simulations. In gas phase, L-asc strongly binds the TiO2 (101) surface as a dianion (L-asc2- ), adopting a bridging bidentate coordination mode (BB), with the two acid protons transferred to two surface 2-fold bridging oxygens (O2c). AIMD simulations show that the interaction between the organic ligand and the anatase surface is stable and comparable to the vacuum one despite the possible solvent effects and/or possible structural distortions of the ligand. In addition, during the AIMD simulations hydroxylation phenomena occur forming transient H3 O+ ions at the solid-liquid interface. For the first time, our results provide insight into the role of the ascorbic acid on the electronic properties of the TiO2 (101), the influence of the water environment on the ligand-surface interaction and the nature of the solid-liquid interface.

Origin of Suppressed Chain Transfer in Phosphinephenolato Ni(II)-Catalyzed Ethylene Polymerization.

Recent breakthroughs in the generation of polar-functionalized and more sustainable degradable polyethylenes have been enabled by advanced phosphinephenolato Ni(II) catalysts. A key has been to overcome this type of catalysts' propensity for extensive chain transfer to enable formation of high-molecular-weight polyethylene chains. We elucidate the mechanistic origin of this paradigm shift by a combined experimental and theoretical study. Single-crystal X-ray structural analysis and cyclic voltammetry of a set of six different catalysts with variable electronics and sterics, combined with extensive pressure reactor polymerization studies, suggest that an attractive Ni-aryl interaction of a P-[2-(aryl)phenyl] is responsible for the suppression of chain transfer. This differs from the established picture of steric shielding found for other prominent late transition metal catalysts. Extensive density functional theory studies identify the relevant pathways of chain growth and chain transfer and show how this attractive interaction suppresses chain transfer.

Catalytic regeneration of metal-hydrides from their corresponding metal-alkoxides via the hydroboration of carbonates to obtain methanol and diols.

Thorium complexes decorated with 5-, 6-, and 7-membered N-heterocyclic iminato ligands containing mesityl wingtip substitutions have been synthesized and fully characterized. These complexes were found to be efficient in the hydroboration of cyclic and linear organic carbonates with HBpin or 9-BBN promoting their decarbonylation and producing the corresponding boronated diols and methanol. In addition, the hydroboration of CO2 breaks the molecule into "CO" and "O" forming boronated methanol and pinBOBpin. Moreover, the demanding depolymerization of polycarbonates to the corresponding boronated diols and methanol opens the possibility of recycling polymers for energy sources. Increasing the core ring size of the ligands allows a better performance of the complexes. The reaction proceeds with high yields under mild reaction conditions, with low catalyst loading, and short reaction times, and shows a broad applicability scope. The reaction is achieved via the recycling of a high-energy Th-H moiety from a stable Th-OR motif. Experimental evidence and DFT calculations corroborate the formation of the thorium hydride species and the reduction of the carbonate with HBpin to the corresponding Bpin-protected alcohols and H3COBpin through the formate and acetal intermediates.

Suzuki-Miyaura Cross-Coupling of Amides by N-C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl2] Catalysts: Reaction Development, Scope, and Mechanism.

The Suzuki-Miyaura cross-coupling of amides by selective N-C acyl bond cleavage represents a powerful tool for constructing biaryl ketones from historically inert amide bonds. These amide bond activation reactions hinge upon efficient oxidative addition of the N-C acyl bond to Pd(0). However, in contrast to the well-researched activation of aryl halides by C(sp2)-X oxidative addition, very few studies on the mechanism of C(acyl)-N bond oxidative addition and catalyst effect have been reported. Herein, we report a study on [Pd(NHC)(sulfide)Cl2] catalysts in amide N-C bond activation. These readily prepared, well-defined, air- and moisture-stable Pd(II)-NHC catalysts feature SMe2 (DMS = dimethylsulfide) or S(CH2CH2)2 (THT = tetrahydrothiophene) as ancillary ligands. The reaction development, kinetic studies, and reaction scope are presented. Extensive DFT studies were conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. We expect that [Pd(NHC)(sulfide)Cl2] precatalysts featuring sulfides as well-defined, readily accessible ancillary ligands will find application in C(acyl)-X bond activation in organic synthesis and catalysis.

A predictive journey towards trans-thioamides/amides.

The cis-trans isomerization of (thio)amides was studied by DFT calculations to get the model for the higher preference for the cis conformation by guided predictive chemistry, suggesting how to select the alkyl/aryl substituents on the C/N atoms that lead to the trans isomer. Multilinear analysis, together with cross-validation analysis, helped to select the best fitting parameters to achieve the energy barriers of the cis to trans interconversion, as well as the relative stability between both isomers. Double experimental check led to the synthesis of the best trans candidate with sterically demanding t-butyl substituents, confirming the utility of predictive chemistry, bridging organic and computational chemistry.

Mechanistic Insights into Ni(II)-Catalyzed Nonalternating Ethylene-Carbon Monoxide Copolymerization.

Polyethylene materials with in-chain-incorporated keto groups were recently enabled by nonalternating copolymerization of ethylene with carbon monoxide in the presence of Ni(II) phosphinephenolate catalysts. We elucidate the mechanism of this long-sought-for reaction by a combined theoretical DFT study of catalytically active species and the experimental study of polymer microstructures formed in pressure-reactor copolymerizations with different catalysts. The pathway leading to the desired nonalternating incorporation proceeds via the cis/trans isomerization of an alkyl-olefin intermediate as the rate-determining step. The formation of alternating motifs is determined by the barrier for the opening of the six-membered C,O-chelate by ethylene binding as the decisive step. An η2-coordination of a P-bound aromatic moiety axially oriented to the metal center is a crucial feature of these Ni(II) catalysts, which also modulates the competition between the two pathways. The conformational constraints imposed in a 2',6'-dimethoxybiphenyl moiety overall result in a desirable combination of disfavoring ethylene coordination along the alternating incorporation pathway, which is primarily governed by electronics, while not overly penalizing the nonalternating chain growth, which is primarily governed by sterics.

Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations.

Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst that is able to bind substrates via the induced fit model according to in-depth computational calculations. The system, which is constituted by an inflexible substrate-recognition site derived from a zinc-porphyrin in the second coordination sphere, features destabilization of ground states as well as stabilization of transition states for the relevant iridium-catalyzed C-H bond borylation of pyridine. In addition, this catalyst appears to be most suited to tightly bind the transition state rather than the substrate. Besides these features, which are reminiscent of the action modes of enzymes, new elementary catalytic steps (i. e. C-B bond formation and catalyst regeneration) have been disclosed owing to the unique distortions encountered in the different intermediates and transition states.

A green route to platinum N-heterocyclic carbene complexes: mechanism and expanded scope.

A sustainable and facile weak-base synthetic route to platinum N-heterocyclic carbene (NHC) complexes is disclosed. The mechanism of this reaction is also elucidated via experimental and computational investigations. This straightforward protocol is then used for the synthesis of novel Pt(II)-NHC complexes and its utility is further explored to access key Pt(0)-NHC precatalysts.

DFT Investigation of Substitutional and Interstitial Nitrogen-Doping Effects on a ZnO(100)-TiO2(101) Heterojunction.

Density Functional Theory (DFT) calculations have been performed to investigate the structural and electronic properties of the ZnO(wurtzite)-ATiO2(anatase) heterojunction in the absence and presence of substitutional, interstitial nitrogen (N) doping and oxygen vacancies (OV). We report a detailed study of the interactions between the two nonpolar ZnO and TiO2 surfaces and on the role of N-doping and oxygen vacancies, which are decisive for improving the photocatalytic activity of the heterojunction. Our calculations show that substitutional N-doping is favored in the ATiO2 portion, whereas the interstitial one is favored in the ZnO region of the interface. Both substitutional and interstitial N-doped sites (i) induce gap states that act as deep electronic traps improving the charge separation and delaying electron-hole recombination, (ii) facilitate the OV formation causing a decrease in the formation energy (E FORM), and (iii) do not affect the band alignment when compared to the undoped analogue system. The presented results shed light on the N-doping effect on the electronic structure of the ZnO(100)-TiO2(101) heterojunction and how N-doping improves its photocatalytic properties.

Straightforward synthesis of [Cu(NHC)(alkynyl)] and [Cu(NHC)(thiolato)] complexes (NHC = N-heterocyclic carbene).

Synthetic access to monomeric copper-alkynyl and copper-thiolato complexes of the type [(NHC)Cu(R)] (R = alkynyl or thiolato) using a weak base approach is reported. All reported reactions proceed under mild conditions in air and in environmentally acceptable solvents. The novel complexes are fully characterized and single crystal X-ray analyses unambiguously establish the atom connectivity in these mononuclear complexes. The importance of the supporting NHC ligand's steric properties in stabilizing mononuclear complexes is discussed.

Neutral Unsymmetrical Coordinated Cyclophane Polymerization Catalysts.

Cyclophane structures can control steric pressure in the otherwise open spaces of square-planar d8 -metal catalysts. This elegant concept was so far limited to symmetrical coordinated metals. We report how a cyclophane motif can be generated in ligands that chelate via two different donors. An ancillary second imine in the versatile κ2 -N,O-salicylaldiminato catalyst type enables ring closure via olefin metathesis and selective double bond hydrogenation to yield a 30-membered ring efficiently. Experimental and theoretical analyses show the ancillary imine is directed away from the active site and inert for catalysis. In ethylene polymerization the cyclophane catalyst is more active and temperature stable vs. an open structure reference, notably also in polar solvents. Increased molecular weights and decreased degrees of branching can be traced to an increased energy of sterically demanding transition states by the encircling cyclophane while chain propagation remains highly efficient.

Biodegradable Polyhydroxyalkanoates by Stereoselective Copolymerization of Racemic Diolides: Stereocontrol and Polyolefin-Like Properties.

Bacterial polyhydroxyalkanoates (PHAs) are a unique class of biodegradable polymers because of their biodegradability in ambient environments and structural diversity enabled by side-chain groups. However, the biosynthesis of PHAs is slow and expensive, limiting their broader applications as commodity plastics. To overcome such limitation, the catalyzed chemical synthesis of bacterial PHAs has been developed, using the metal-catalyzed stereoselective ring-opening (co)polymerization of racemic cyclic diolides (rac-8DLR , R=alkyl group). In this combined experimental and computational study, polymerization kinetics, stereocontrol, copolymerization characteristics, and the properties of the resulting PHAs have been examined. Most notably, stereoselective copolymerizations of rac-8DLMe with rac-8DLR (R=Et, Bu) have yielded high-molecular-weight, crystalline isotactic PHA copolymers that are hard, ductile, and tough plastics, and exhibit polyolefin-like thermal and mechanical properties.

Control of Chain Walking by Weak Neighboring Group Interactions in Unsymmetrical Catalysts.

A combined theoretical and experimental study shows how weak attractive interactions of a neighboring group can strongly promote chain walking and chain transfer. This accounts for the previously observed very different microstructures obtained in ethylene polymerization by [κ2-N,O-{2,6-(3',5'-R2C6H3)2C6H3-N═C(H)-(3,5-X,Y-2-O-C6H2)}NiCH3(pyridine)], namely hyperbranched oligomers for remote substituents R = CH3 versus high-molecular-weight polyethylene for R = CF3. From a full mechanistic consideration, the alkyl olefin complex with the growing chain cis to the salicylaldiminato oxygen donor is identified as the key species. Alternative to ethylene chain growth by insertion in this species, decoordination of the monomer to form a cis ß-agostic complex provides an entry into branching and chain-transfer pathways. This release of monomer is promoted and made competitive by a weak η2-coordination of the distal aryl rings to the metal center, operative only for the case of sufficiently electron-rich aryls. This concept for controlling chain walking is underlined by catalysts with other weakly coordinating furan and thiophene motifs, which afford highly branched oligomers with >120 branches per 1000 carbon atoms.

Hydroxylamine-induced oxidation of ferrous carbonylated truncated hemoglobins from Mycobacterium tuberculosis and Campylobacter jejuni is limited by carbon monoxide dissociation.

Hydroxylamine (HA) is an oxidant of ferrous globins and its action has been reported to be inhibited by CO, even though this mechanism has not been clarified. Here, kinetics of the HA-mediated oxidation of ferrous carbonylated Mycobacterium tuberculosis truncated hemoglobin N and O (Mt-trHbN(II)-CO and Mt-trHbO(II)-CO, respectively) and Campylobacter jejuni truncated hemoglobin P (Cj-trHbP(II)-CO), at pH 7.2 and 20.0 °C, are reported. Mixing Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO solution with the HA solution brings about absorption spectral changes reflecting the disappearance of the ferrous carbonylated derivatives with the concomitant formation of the ferric species. HA oxidizes irreversibly Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO with the 1:2 stoichiometry. The dissociation of CO turns out to be the rate-limiting step for the oxidation of Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO by HA. Values of the second-order rate constant for HA-mediated oxidation of Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO range between 8.8 × 104 and 8.6 × 107 M-1 s-1, reflecting different structural features of the heme distal pocket. This study (1) demonstrates that the inhibitory effect of CO is linked to the dissociation of this ligand, giving a functional basis to previous studies, (2) represents the first comparative investigation of the oxidation of ferrous carbonylated bacterial 2/2 globins belonging to the N, O, and P groups by HA, (3) casts light on the correlation between kinetics of HA-mediated oxidation and carbonylation of globins, and (4) focuses on structural determinants modulating the HA-induced oxidation process.

The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways.

α-Methylene-γ-butyrolactone (MBL), a naturally occurring and biomass-sourced bifunctional monomer, contains both a highly reactive exocyclic C═C bond and a highly stable five-membered γ-butyrolactone ring. Thus, all previous work led to exclusive vinyl-addition polymerization (VAP) product P(MBL)VAP. Now, this work reverses this conventional chemoselectivity to enable the first ring-opening polymerization (ROP) of MBL, thereby producing exclusively unsaturated polyester P(MBL)ROP with Mn up to 21.0 kg/mol. This elusive goal was achieved through uncovering the thermodynamic, catalytic, and processing conditions. A third reaction pathway has also been discovered, which is a crossover propagation between VAP and ROP processes, thus affording cross-linked polymer P(MBL)CLP. The formation of the three types of polymers, P(MBL)VAP, P(MBL)CLP, and P(MBL)ROP, can be readily controlled by adjusting the catalyst (La)/initiator (ROH) ratio, which is determined by the unique chemoselectivity of the La-X (X = OR, NR2, R) group. The resulting P(MBL)ROP is degradable and can be readily postfunctionalized into cross-linked or thiolated materials but, more remarkably, can also be fully recycled back to its monomer thermochemically. Computational studies provided the theoretical basis for, and a mechanistic understanding of, the three different polymerization processes and the origin of the chemoselectivity.

Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization.

A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. PdII -catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates α,ω-di-furan telechelic polyethylene. Orthogonally reactive exclusively in-chain anhydride groups are formed by terpolymerization with carbic anhydride. Combined experimental and theoretical DFT studies reveal the key for this direct approach to telechelics to be a match of the comonomers' different electronics and bulk. Identified essential features of the comonomer are that it is an electron-rich olefin that forms an insertion product stabilized by an additional interaction, namely a π-η3 interaction for the case of VF.

Robust Cross-Linked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization.

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust cross-linked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site-controlled propagation mechanism. Postfunctionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible cross-linked thin-film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Cross-linking of such complexes affords robust cross-linked stereocomplexes that are solvent-resistant and also exhibit considerably enhanced thermal and mechanical properties compared with the un-cross-linked stereocomplexes.

Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes.

Gold(I) dicarbene complexes [Au2 (MeIm-Y-ImMe)2 ](PF6 )2 (Y=CH2 (1), (CH2 )2 (2), (CH2 )4 (4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2 -ImMe)2 AuI2 ](PF6 )2 (1 a(I) ) and the gold(III) complexes [Au2 I4 (MeIm-Y-ImMe)2 ](PF6 )2 (2 c(I) and 4 c(I) ). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2 Cl4 (MeIm-CH2 -ImMe)2 ](PF6 )2 (1 c(Cl) ) and [Au2 Cl4 (MeIm-(CH2 )2 -ImMe)2 ](Cl)2 (2 c(Cl) -Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2 , Br2 and I2 to give the successive formation of the mixed-valence gold(I)/gold(III) n a(X) and gold(III) n c(X) (excluding compound 1 c(I) ) complexes. However, complex 3 affords with Cl2 and Br2 the gold(II) complex 3 b(X) [Au2 X2 (MeIm-(CH2 )3 -ImMe)2 ](PF6 )2 (X=Cl, Br), which is the predominant species over compound 3 c(X) even in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations.