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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 379 records · Page 21
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DOE OSTI2022

Four-Coordinate Fe N 2 and Imido Complexes Supported by a Hemilabile NNC Heteroscorpionate Ligand

Inspired by mechanistic proposals for N 2 reduction at the nitrogenase FeMo cofactor, we report herein a new, strongly σ-donating heteroscorpionate ligand featuring two weak-field pyrazoles and an alkyl donor. This ligand supports four-coordinate Fe(I)-N 2 , Fe(II)-Cl, and Fe(III)-imido complexes, which we have characterized using a variety of spectroscopic and computational methods. Structural and quantum mechanical analysis reveal the nature of the Fe–C bonds to be essentially invariant between the complexes, with conversion between the (formally) low-valent Fe-N 2 and high-valent Fe-imido complexes mediated by pyrazole hemilability. This presents a useful strategy for substrate reduction at such low-coordinate centers and suggests a mechanism by which FeMoco might accommodate the binding of both π-acidic and π-basic nitrogenous substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Lewis Acids and Electron-Withdrawing Ligands Accelerate CO Coordination to Dinuclear Cu I Compounds

A series of dinuclear molecular copper complexes were prepared and used to model the binding and Lewis acid stabilization of CO in heterogeneous copper CO 2 reduction electrocatalysts. Experimental studies (including measurement of rate and equilibrium constants) and electronic structure calculations suggest that the key kinetic barrier for CO binding may be a σ-interaction between CuI and the incoming CO ligand. The rate of CO coordination can be increased upon the addition of Lewis acids or electron-withdrawing substituents on the ligand backbone. Conversely, K eq for CO coordination can be increased by adding electron density to the metal centers of the compound, consistent with stronger π-backbonding. Lastly, the electrochemically measured kinetic results were mapped onto an electrochemical zone diagram to illustrate how these system changes enabled access to each zone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Ligand–Metal Complementarity in Rare-Earth and Actinide Chemistry

In this article, the rare-earths are comprised of scandium, yttrium, and the lanthanides (atomic numbers 21, 39, and 57–71). (1) While these elements are essential to modern life, they were historically characterized as simple, perhaps dull, compared to the rich multielectron chemistry of d-block metals in catalysts and enzymes. These descriptions were quite fair and largely true at the time that these elements were being discovered and the first compounds containing them were being synthesized, although much progress has been made to overturn this view of the rare earths. Similarly, discussions about actinide chemistry are sometimes limited to research pertinent to the nuclear industry, which, while comprising technologies vital to modern society, does not celebrate the fascinating chemical space that much of the actinide series occupies. These historic characterizations of most of the rare-earth and actinide elements persist in some textbooks, and we acknowledge that it is a helpful place to start; however, altogether these series comprise 32 elements-27% of the 118 known by 2024-and we suggest it would be an unfortunate twist of physics if such a large proportion of the Periodic Table were genuinely dull. Indeed, as this Inorganic Chemistry Forum Issue “Ligand-Metal Complementarity in Rare-Earth and Actinide Chemistry” highlights, the chemistry-let alone the physics, that is, spectroscopy and magnetism-of these elements is rich and depends on ligands!

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

tinyIFD: A High-Throughput Binding Pose Refinement Workflow Through Induced-Fit Ligand Docking

A critical step in structure-based drug discovery is predicting whether and how a candidate molecule binds to a model of a therapeutic target. However, substantial protein side chain movements prevent current screening methods, such as docking, from accurately predicting the ligand conformations and require expensive refinements to produce viable candidates. Here, we present the development of a high-throughput and flexible ligand pose refinement workflow, called “tinyIFD”. The main features of the workflow include the use of specialized high-throughput, small-system MD simulation code mdgx.cuda and an actively learning model zoo approach. We show the application of this workflow on a large test set of diverse protein targets, achieving 66% and 76% success rates for finding a crystal-like pose within the top-2 and top-5 poses, respectively. We also applied this workflow to the SARS-CoV-2 main protease (M pro ) inhibitors, where we demonstrate the benefit of the active learning aspect in this workflow.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Exploring Ligand-to-Metal Charge-Transfer States in the Photo-Ferrioxalate System Using Excited-State Specific Optimization

The photo-ferrioxalate system (PFS), [Fe(III)(C 2 O 4 )] 3– , more than an exact chemical actinometer, has been extensively applied in wastewater and environment treatment. Despite many experimental efforts to improve clarity, important aspects of the mechanism of ferrioxalate photolysis are still under debate. In this paper, we employ the recently developed WΓ-CASSCF to investigate the ligand-to-metal charge-transfer states that are key to ferrioxalate photolysis. This investigation provides a qualitative picture of these states and key potential energy surface features related to the photolysis. Furthermore, our theoretical results are consistent with the prompt charge-transfer picture seen in recent experiments and clarify some features that are not visible in experiments. Two ligand-to-metal charge-transfer states contribute to the photolysis of ferrioxalate, and the avoided crossing barrier between them is low compared with the initial photoexcitation energy. Our data also clarify that one Fe–O bond cleaves first, followed by the C–C bond and the other Fe–O bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Origin of Stabilization of Ligand-Centered Mixed Valence Ruthenium Azopyridine Complexes: DFT Insights for Neuromorphic Applications

Redox-driven conductance changes are critical processes in molecular- and coordination-complex-based memristive thin films and devices that are envisioned for neuromorphic technologies, but fundamental mechanisms of conductance switching are not fully understood. Here, we explore charge disproportionation (CD) processes in [Ru II L 2 ](PF 6 ) 2 molecular systems that intrinsically involve interfragment charge transfer (IFCT). Using a combination of ab initio molecular dynamics simulation (AIMD), time-dependent density functional theory (TD-DFT), and density functional theory (DFT) calculations, we investigate the electron transfer mechanisms and the roles of temperature and cell volumetric expansion in facilitating the counterion movements and electronic transitions required for low-cost IFCT and charge redistribution. A detailed analysis of the density of states and TD-DFT calculations highlights that unpaired electrons play a crucial role in low-energy transitions, with the azo (N=N) groups of the ligand serving as the primary sites for electronic transport between molecular fragments, further stabilizing the asymmetric state. Localization of added electrons on azo ligands occurs with negligible change at the Ru centers, supported by atomic volume expansions up to +4.74 bohr 3 , and goes along with a progressive reduction of the HOMO−LUMO gap across redox states, suggesting enhanced conductivity. The TD-DFT analysis reveals a dominant IFCT excitation at 2082.76 nm in the doubly reduced (22) state, while a stabilization energy of 1.20 eV of the asymmetric (13) state relative to the symmetric (22) state is predicted by constrained DFT. Periodic DFT and AIMD simulations emulating a molecular film show that the stabilization of the asymmetric state, relative to a symmetric one, translates in net charge separation values (order of ∼0.33 e) that are strongly linked to increased counterion mobility (average counterion displacements exceeding 0.7 Å per atom during CD events) and the involvement of azo groups in electron redistribution. These findings, which align with previously reported experimental and computational data, provide key insights into the IFCT mechanisms and electronic transport facilitated by azo groups, with important implications for redox-driven memristive and neuromorphic technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ligand-Free Processable Perovskite Semiconductor Ink

We report traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs 2 TeX 6 (X = Cl - , Br - , I - ) in polar aprotic solvents, leading to the stabilization of isolated [TeX 6 ] 2- octahedral anions and free Cs + cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multifunctional inks with the ability to reversibly transform between the liquid ink and the solid-state perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, spraying or painting, and stamping, highlighting the crucial role of solvated octahedral complexes toward the rapid formation of phase-pure perovskite structures in ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Comparisons of bpy and phen Ligand Backbones in Cr-Mediated (Co-)Electrocatalytic CO 2 Reduction

Due to the rise in atmospheric carbon dioxide (CO 2 ) concentrations, there is a need for the development of new strategies to enhance the selectivity and activity of the electrocatalytic conversion of CO 2 to value-added products. The incorporation of redox mediators (RMs) as co-catalysts to enhance the transfer of redox equivalents during catalysis has been gaining more attention in recent years across a variety of small molecule transformations. We have shown that using Cr-centered complexes with sulfone-based RMs leads to an enhancement of CO 2 reduction electrocatalysis under protic conditions via an inner-sphere mechanism. In these co-catalytic systems, an oxygen atom of the reduced RM binds to the Cr center to form a key intermediate stabilized by pancake bonding between the reduced aromatic components of the catalyst ligand backbone and the RM. This interaction facilitates the transfer of an electron and accesses a more kinetically favorable reaction pathway. Here, we show that expanding the aromatic character of the ligand backbone of the catalyst as well as the RM can cause a greater enhancement of co-electrocatalytic activity. These results suggest that further activity improvements can be achieved by focusing on the kinetic and thermodynamic parameters which control association between the catalyst and RM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C–H Activation

High-valent iron complexes play a crucial role in the oxidation of organic substrates, especially in C–H bond functionalization reactions in biology. This paper investigates the reactivity of nonporphyrin tripodal ligands featuring a secondary coordination sphere, focusing on their prospective ability to stabilize high-valent iron-oxo species. Using NMR spectroscopy and X-ray crystallography, we detail the formation of an Fe(III)-alkoxide complex through intramolecular C–H bond activation, providing insight into the potential transient formation of a high-valent iron-oxo intermediate. While attempts to observe an Fe(IV)-oxo complex were unsuccessful, our findings underscore the significance of the ligand electronic environment in stabilizing reactive iron species for C–H bond activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

CO 2 Hydrogenation and Formic Acid Dehydrogenation Using Ir Catalysts with Amide-Based Ligands

In this work, a series of Ir catalysts bearing amide-based ligands generated by a deprotonated amide moiety was prepared with the hypotheses that the strong electron-donating ability of the coordinated anionic nitrogen atom and the proton-responsive OH group near the metal center will improve the catalytic activity for CO 2 hydrogenation and formic acid (FA) dehydrogenation. The effects of the modifications of the ligand architecture on the catalytic activity were investigated for CO 2 hydrogenation at ambient conditions (25 °C with 0.1 MPa H 2 /CO 2 (v/v = 1/1)) and under slightly harsher conditions (50 °C with 1.0 MPa H 2 /CO 2 ) in basic aqueous solutions together with deuterium kinetic isotope effects (KIEs) with selected catalysts. Cp*Ir( L12 )(H 2 O)HSO 4 ( L12 = 6-hydroxy- N -phenylpicolinamidate) that has an anionic coordinating N atom and an OH group in the second coordination sphere, exhibits a turnover frequency (TOF) of 198 h –1 based on the initial 1 h of reaction. This TOF which, to the best of our knowledge, is the highest value ever reported under ambient conditions in basic aqueous solutions. However, Cp*Ir( L10 )(H 2 O)HSO 4 ( L10 = (4-hydroxy- N -methylpicolinamidate) performs better in long-term CO 2 hydrogenation (up to a TON of 14 700 with [Ir] = 10 μM after 348 h and the final formate concentration of 0.643 M with [Ir] = 250 μM) at ambient conditions. Further, the catalytic activity for FA dehydrogenation was examined under three different conditions (pH 1.6, 2.3, and 3.5). The Cp*Ir( L12 )(H 2 O)HSO 4 complex in any of these conditions is less active compared to the picolinamidate catalysts without ortho -OH, owing to its instability. The complex without OH group, Cp*Ir( L8 )(H 2 O)HSO 4 ( L8 = N -phenyl-picolinamidate), exhibits a high TOF (up to 118 000 h -1 ) at 60 °C. Theoretical calculations were performed to examine the catalytic mechanism, and a step-by-step mechanism has been proposed for both CO 2 hydrogenation and FA dehydrogenation reactions. Density functional theory calculations of [Cp*Ir( L3 )(H 2 O)]HSO 4 ( L3 = picolinamidate) and the X-ray structure of the [Cp*Ir( L7 )(H)]·H 2 O ( L7 = N -methylpicolinamidate) complex imply a pH-dependent conformational change from N , N coordination to N , O coordination upon lowering the pH of the aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Strong NIR II Chiroptical Response and Magnetic Anisotropy via Modular Installation of Chiral Capping Ligands on a Light-Emitting Diradicaloid Scaffold

Low-energy molecular lumiphores have seen increased interest due to potential imaging and communications applications. Specifically, molecules that emit in the near-infrared (NIR, 700–1700 nm) or telecom (∼1260–1625 nm) regions, where attenuation is minimized in biological tissue and optical fibers, respectively, can drastically improve image resolution and depth penetration; however, bright low-energy emission is rare due to exponentially decreasing quantum yields in this region. Chiral molecules exhibiting strong NIR or telecom absorption/emission would be of particular interest due to advanced security and spintronics applications, but these compounds remain scarce and are currently restricted to lanthanide or nanoparticle-based systems. Here, we report the synthesis of a chiral organic-based NIR emitter, enabled by simple peripheral installation of chiral capping ligands. These ligands twist the achiral NIR-emissive core, breaking inversion symmetry. Furthermore, this twisting enables strong chiroptical responses observed via static and transient circular dichroism and increased magnetic anisotropy through electron paramagnetic resonance (EPR) measurements, establishing this strategy as a promising method for the development of new chiral emitters and sensors.

Electron paramagnetic resonance spectroscopy↗
DOE OSTI2024

Triplet Management at Ligand-Perovskite Interface to Enhanced Photovoltaics Performance

Aromatic organic molecules are widely used as passivators in perovskite solar cells (PSCs). Efforts have been devoted to improving the energy alignments, band edge states, and defect passivation functionalities. However, potential energy loss through triplet states in such conjugated molecules has not been investigated in the past. Here, we report the observation of charge transfer from FAPbI 3 to the triplet state of a pyrene (Pyr)-based cationic ligand. Such a potential loss channel can be suppressed via delicate triplet management in polycyclic aromatic compounds. Interestingly, a subtle structural modification from Pyr to the triphenylene (TP) core gave rise to shallower triplets that prohibit electron transfer from perovskites. This strategy has led to TP-passivated PSCs achieving an enhanced power conversion efficiency (PCE) of 24.69% from 23.10% in Pyr-passivated counterparts. Moreover, the devices retained above 80% initial PCE after 4000 h of light soaking, which likely benefited from the reduced triplet electron trapping at the ligand-perovskite interface.

14 SOLAR ENERGY↗
DOE OSTI2021

Pyroelectricity of Lead Sulfide (PbS) Quantum Dot Films Induced by Janus-Ligand Shells

Asymmetry is an essential property to control. To do that in nanocrystalline systems we have developed methods to produce Janus-ligand shells on otherwise symmetric PbS quantum dots (QDs). In this work, we demonstrate that control by constructing a system that exhibits pyroelectricity built from spherical PbS QDs. We observed a pyroelectric current in two different configurations. In one configuration, the QDs are self-assembled into close-packed arrays while in the second configuration, the QDs are dispersed into an electro-inactive polymer, polydimethylsiloxane. Both exhibit a pyroelectric response. In the first configuration we estimate a lower limit of the pyroelectric coefficient to be 1.97 × 10 -7 C/m 2 K, which is likely limited by the degree of QD alignment during film formation but is already on par with common pyroelectric systems. Compared with inorganic ceramic-like and polymeric pyroelectric materials, pyroelectric films self-assembled from polar QDs are easier to prepare, responsive to light with different energies based on QD exciton energy, and the polarization of each QD could be easily tuned by constructing different Janus-ligand shells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structure and Reactivity of a High-Spin, Nonheme Iron(III)- Superoxo Complex Supported by Phosphinimide Ligands

Nonheme iron oxygenases utilize dioxygen to accomplish challenging chemical oxidations. Additionally, a further understanding of the Fe-O 2 intermediates implicated in these processes is challenged by their highly transient nature. To that end, we have developed a ligand platform featuring phosphinimide donors intended to stabilize oxidized, high-spin iron complexes. O 2 exposure of single crystals of a three-coordinate Fe(II) complex of this framework allowed for in crystallo trapping of a terminally bound Fe-O 2 complex suitable for XRD characterization. Spectroscopic and computational studies of this species support a high-spin Fe(III) center antiferromagnetically coupled to a superoxide ligand, similar to that proposed for numerous nonheme iron oxygenases. In addition to the apparent stability of this synthetic Fe-O 2 complex, its ability to engage in a range of stoichiometric and catalytic oxidation processes demonstrates that this iron-phosphinimide system is primed for development in modeling oxidizing bioinorganic intermediates and green oxidation chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal–Ligand Cooperativity

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [Co III Cp(P Ph 2 N Bn 2 )(CH 3 CN)] 2+ to [HCo III Cp(P Ph 2 NBn 2 )] + . This complex catalytically converts CO 2 to formate under CO 2 reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the P Ph 2 N Bn 2 ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation. We reveal three unique PCET mechanisms, and we show that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site en route to the thermodynamically favored cobalt hydride. Cyclic voltammograms recorded with proton sources that span a wide range of pK a values show four distinct regimes where the mechanism changes as a function of acid strength, acid concentration, and timescale between electrochemical steps. Peak shift analysis was used to determine proton transfer rate constants where applicable. Furthermore, this work highlights the astute choices that must be made when designing catalytic systems, including the basicity and kinetic accessibility of protonation sites, acid strength, acid concentration, and timescale between electron transfer steps, to maximize catalyst stability and efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Photocatalytic Ammonia Synthesis using Fe-Based MOFs: The Role of Ligand Functionalization

Photocatalytic ammonia (NH 3 ) synthesis offers a carbon-neutral alternative to the Haber−Bosch process, which generates 42 million metric tons of CO 2 equivalent emissions annually. However, solar-to-ammonia conversion with contemporary photocatalysts remains far from practical requirements, and understanding the limiting factors in systems with well-defined active sites is crucial. Here, we show how the μ 3 -oxo-centered trinuclear Fe cluster in MIL-101(Fe) functions as the catalytic motif for N 2 -to-NH 3 conversion through combined experimental and computational investigations. Comparative studies with a molecular analogue demonstrate that the cluster is stabilized within the MOF framework, sustaining redox cycling and maintaining high catalytic activity. We systematically functionalized the dicarboxylate ligands of MIL-101(Fe) with −NH 2 , −Br, −NO 2 , −F, and −CF 3 to probe how ligand chemistry modulates Fe electron density, N 2 adsorption capacity, and proton availability, correlating these properties with catalytic performance using spectroscopic and surface characterization techniques alongside timeresolved infrared to assess excited-state lifetimes. F-functionalization optimally balances N 2 activation, proton availability at Fe active sites, and excited-state lifetimes, boosting NH 3 production by ∼ 60% relative to unmodified MIL-101(Fe). This study of ligandfunctionalized MIL-101(Fe) MOFs uncovers the underlying structure-activity relationships and advances design principles for solardriven NH 3 synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis

A new Ru complex containing the deprotonated 2,2':6',2"-terpyridine-6,6"-diphosphonic acid (H 4 tPa) and pyridine (py) of general formula [Ru II (H 3 tPa-κ-N 3 O)(py) 2 ] + , 2 + , has been prepared and thoroughly characterized by means of spectroscopic and electrochemical techniques, X-ray diffraction analysis, and density functional theory (DFT) calculations. Complex 2 + presents a dynamic behavior in the solution that involves the synchronous coordination and the decoordination of the dangling phosphonic groups of the tPa 4– ligand. Yet, at oxidation state IV, complex 2 + becomes seven coordinated with the two phosphonic groups now bonded to the metal center. Further, at this oxidation state at neutral and basic pH, the Ru complex undergoes the coordination of an exogenous OH – group from the solvent that leads to an intramolecular aromatic O atom insertion into the CH bond of one of the pyridyl groups, forming the corresponding phenoxo-phosphonate Ru complex [Ru III (tPaO-κ-N 2 O P O C )(py) 2 ] 2– , 4 2– , where tPaO 5– is the 3-(hydroxo-[2,2':6',2"-terpyridine]-6,6"-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 4 2– , has been isolated and spectroscopically and electrochemically characterized. In addition, a crystal structure has been also obtained using single-crystal X-ray diffraction techniques. Complex 4 2– turns out to be an exceptional water oxidation catalyst achieving record maximum turnover frequencies (TOF max ) on the order of 16 000 s –1 . A mechanistic analysis complemented with DFT calculations has further been carried out, showing the critical role of intramolecular second coordination sphere effects exerted by the phosphonate groups in lowering the activation energy at the rate-determining step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

CO oxidation over a ligand coordinated single site Rh catalyst: identification of the active complex

Single atom catalysis has evolved as a promising strategy to enhance atom utilization efficiency, lower reaction temperatures, and control reaction pathways in heterogeneous catalytic reactions. An important challenge using supported single atom catalysts is the stability of metal single atoms during reactions. Here, we present an approach to stabilize single rhodium atoms on a titania support via a metal–ligand coordination strategy. We explore the reaction activity and mechanism of CO oxidation, as well as the stability under oxidative reaction conditions. Kinetic studies suggest that, with an excess of oxygen in the feed gas, oxygen activation is more facile on defective titania surfaces than on pristine titania surfaces. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis shows that on the pristine titania surface, the 1,10-phenanthroline-5,6-dione (PDO) coordinated Rh catalyst (Rh–PDO/TiO 2 ) catalyzes CO oxidation via the formation of carbonate-like species, which is similar to what occurs on Rh nanoparticle catalysts. However, on the defective titania surface, no carbonate species form for Rh–PDO/def-TiO 2 . The supported Rh–ligand catalysts are also shown to be very stable in such a reaction environment at elevated temperatures, potentially allowing for wide applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗