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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Optimized Substrate Positioning Enables Switches in the C–H Cleavage Site and Reaction Outcome in the Hydroxylation–Epoxidation Sequence Catalyzed by Hyoscyamine 6β-Hydroxylase

Hyoscyamine 6β-hydroxylase (H6H) is an Fe(II)- and 2-oxoglutarate-dependent (Fe/2OG) oxygenase that catalyzes the last two steps in the biosynthesis of scopolamine, a prolifically administered anti-nausea drug. After its namesake first reaction, H6H couples the newly installed C6-bonded oxygen to C7 to form the epoxide of scopolamine. Oxoiron(IV) (ferryl) intermediates initiate both reactions by cleaving C–H bonds, but it remains unclear how the enzyme switches target site and promotes (C6)O–C7 coupling in preference to C7 hydroxylation in the second step. In one possible epoxidation mechanism, the C6 oxygen would – analogously to mechanisms proposed for the Fe/2OG halogenases and, in the preceding paper, N-acetylnorloline synthase (LolO) – coordinate as alkoxide to the C7–H-cleaving ferryl intermediate to enable alkoxyl coupling to the ensuing C7 radical. Here we provide structural and kinetic evidence that H6H instead exploits the distinct spatial dependencies of competitive C–H-cleavage (C6 vs C7) and C–O-coupling (oxygen rebound vs cyclization) steps to promote the two-step sequence without substrate coordination or repositioning for the epoxidation step. Structural comparisons of ferryl-mimicking vanadyl complexes of wild-type H6H and a variant that preferentially hydroxylates C7 of 6-hydroxyhyoscyamine suggest that only a modest (~ 10°) shift in the Fe–O–H(C7) approach angle is sufficient to change the outcome. Finally, the observation that, in wild-type H6H, 2 H 2 O solvent also increases the C7-hydroxylation:epoxidation ratio by ~ 8-fold implies that the latter outcome requires cleavage of the alcohol O-H bond, which, unlike in the LolO oxacyclization, is not accomplished in advance of C–H cleavage.

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

Design principles of tandem cascade photoelectrochemical devices

Cascade photoelectrocatalysis (PEC) is a possible method to improve the selectivity of solar-driven CO 2 reduction (CO 2 R). This concept can be realized by coupling different CO 2 R catalysts to different subcells in a multijunction photovoltaic (PV) stack. Efficient implementation will require careful tuning of the photocurrents and design of the photovoltages provided by the subcells to the CO 2 R catalysts in such a way as to facilitate the target reaction. Here, we outline the design principles of the tandem PEC approach using two-step conversion of CO 2 to ethylene in aqueous electrolyte, via a CO intermediate, as a model system. To perform this reaction, the first coupled PV-catalyst component should provide 4 electrons to reduce 2 molecules of CO 2 to CO; the second component should provide 8 electrons to reduce 2 CO molecules to C 2 H 4 . Based on known CO 2 R catalysts, the overpotential required to produce CO can be less than that required to reduce it to ethylene, creating the opportunity for improved efficiency. Cascade PEC can be realized in a three-terminal tandem (3TT) configuration using III–V-semiconductor based subcells coupled to Au (produces CO intermediate) and Cu (converts CO to ethylene). The current to each catalyst can be controlled by the area of the subcell exposed to the electrolyte, and the photovoltage is determined by the materials selected and device configuration. Operating conditions are found by simulating the coupled system using the open-source circuit simulator SPICE (Simulation Program with Integrated Circuits Emphasis). We identify conditions under which a 3TT configuration can have a higher solar to chemical conversion efficiency compared to a two-terminal two-junction tandem (2T 2J) with the same absorbers and a Cu catalyst only. We also show that 3TT PEC devices can be less sensitive to variations in catalyst activity compared to 2T devices. Lastly, we discuss the applications of cascade PEC to CO 2 reduction, using different intermediates, and to other chemical networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Nonlocal correlations in the orbital selective Mott phase of a one-dimensional multiorbital Hubbard model

Here, we study nonlocal correlations in a three-orbital Hubbard model defined on an extended one-dimensional chain using determinant quantum Monte Carlo and density matrix renormalization group methods. We focus on a parameter regime with robust Hund's coupling, which produces an orbital selective Mott phase (OSMP) at intermediate values of the Hubbard U , as well as an orbitally ordered ferromagnetic insulating state at stronger coupling. An examination of the orbital- and spin-correlation functions indicates that the orbital ordering occurs before the onset of magnetic correlations in this parameter regime as a function of temperature. In the OSMP, we find that the self-energy for the itinerant electrons is momentum dependent, indicating a degree of nonlocal correlations while the localized electrons have largely momentum independent self-energies. These nonlocal correlations also produce relative shifts of the holelike and electronlike bands within our model. The overall momentum dependence of these quantities is strongly suppressed in the orbitally ordered insulating phase.

36 MATERIALS SCIENCE↗
DOE OSTI2010

A fundamental test of the Higgs Yukawa coupling atRHIC in A+A collisions

Searches for the intermediate boson, W{sup {+-}}, the heavy quantum of the Weak Interaction, via its semi-leptonic decay, W {yields} e+v, in the 1970's instead discovered unexpectedly large hadron production at high p{sub T}, notably {pi}{sup 0}, which provided a huge background of e{sup {+-}} from internal and external conversions. Methods developed at the CERN ISR which led to the discovery of direct-single-e{sup {+-}} in 1974, later determined to be from the semi-leptonic decay of charm which had not yet been discovered, were used by PHENIX at RHIC to make precision measurements of heavy quark production in p-p and Au+Au collisions, leading to the puzzle of apparent equal suppression of light and heavy quarks in the QGP. If the Higgs mechanism gives mass to gauge bosons but not to fermions, then a proposal that all 6 quarks are nearly massless in a QGP, which would resolve the puzzle, can not be excluded. This proposal can be tested with future measurements of heavy quark correlations in A+A collisions.

43 PARTICLE ACCELERATORS↗
DOE OSTI2016

A surface ice module for wind turbine dynamic response simulation using FAST

It is a fact that developing offshore wind energy has become more and more serious worldwide in recent years. Many of the promising offshore wind farm locations are in cold regions that may have ice cover during wintertime. The challenge of possible ice loads on offshore wind turbines raises the demand of modeling capacity of dynamic wind turbine response under the joint action of ice, wind, wave, and current. The simulation software FAST is an open source computer-aided engineering (CAE) package maintained by the National Renewable Energy Laboratory. In this paper, a new module of FAST for assessing the dynamic response of offshore wind turbines subjected to ice forcing is presented. In the ice module, several models are presented which involve both prescribed forcing and coupled response. For conditions in which the ice forcing is essentially decoupled from the structural response, ice forces are established from existing models for brittle and ductile ice failure. For conditions in which the ice failure and the structural response are coupled, such as lock-in conditions, a rate-dependent ice model is described, which is developed in conjunction with a new modularization framework for FAST. In this paper, analytical ice mechanics models are presented that incorporate ice floe forcing, deformation, and failure. For lower speeds, forces slowly build until the ice strength is reached and ice fails resulting in a quasi-static condition. For intermediate speeds, the ice failure can be coupled with the structural response and resulting in coinciding periods of the ice failure and the structural response. A third regime occurs at high speeds of encounter in which brittle fracturing of the ice feature occurs in a random pattern, which results in a random vibration excitation of the structure. An example wind turbine response is simulated under ice loading of each of the presented models. This module adds to FAST the capabilities for analyzing the response of wind turbines subjected to forces resulting from ice impact on the turbine support structure. The conditions considered in this module are specifically addressed in the International Organization for Standardization (ISO) standard 19906:2010 for arctic offshore structures design consideration. Special consideration of lock-in vibrations is required due to the detrimental effects of such response with regard to fatigue and foundation/soil response. Finally, the use of FAST for transient, time domain simulation with the new ice module is well suited for such analyses.

17 WIND ENERGY↗
DOE OSTI2024

Full‐dimensional coupled‐channel statistical approach to atom‐triatom systems and applications to H/D + O 3 reaction

Abstract The statistical quantum model (SQM), which assumes that the reactivity is controlled by entrance/exit channel quantum capture probabilities, is well suited for chemical reactions with a long‐lived intermediate complex. In this work, a time‐independent coupled‐channel implementation of the SQM approach is developed for atom‐triatom systems in full dimensionality. As SQM treats the capture dynamics quantum mechanically, it is capable of handling quantum effects such as tunneling. A detailed study of the H/D + O 3 capture dynamics was performed by applying the newly developed SQM method on an accurate global potential energy surface. Agreement with previous ring polymer molecular dynamics (RPMD) results on the same potential energy surface is excellent except for very low temperatures. The SQM results are also in reasonably good agreement with available experimental rate coefficients. The strong H/D kinetic isotope effect underscores the dominant role of quantum tunneling under an entrance channel barrier at low temperatures.

Yang, Dongzheng↗
DOE OSTI2020

Bimetallics in a Nutshell: Complexes Supported by Chelating Naphthyridine-Based Ligands

Bimetallic motifs are a structural feature common to some of the most effective and synthetically useful catalysts known, including in the active sites of many metalloenzymes and on the surfaces of industrially relevant heterogeneous materials. However, the complexity of these systems often hampers detailed studies of their fundamental properties. To glean valuable mechanistic insight into how these catalysts function, this research group has prepared a family of dinucleating 1,8-naphthyridine ligands that bind two first-row transition metals in close proximity, originally designed to help mimic the proposed active site of metal oxide surfaces. Of the various bimetallic combinations examined, dicopper(I) is particularly versatile, as neutral bridging ligands adopt a variety of different binding modes depending on the configuration of frontier orbitals available to interact with the Cu centers. Organodicopper complexes are readily accessible, either through the traditional route of salt metathesis or via the activation of tetraarylborate anions through aryl group abstraction by a dicopper(I) unit. The resulting bridging aryl complexes engage in C-H bond activations, notably with terminal alkynes to afford bridging alkynyl species. In this work, the μ-hydrocarbyl complexes are surprisingly tolerant of water and elevated temperatures. This stability was leveraged to isolate a species that typically represents a fleeting intermediate in Cu-catalyzed azide-alkyne coupling (CuAAC); reaction of a bridging alkynyl complex with an organic azide afforded the first example of a well-defined, symmetrically bridged dicopper triazolide. This complex was shown to be an intermediate during CuAAC, providing support for a proposed bimetallic mechanism. These platforms are not limited to formally low oxidation states; chemical oxidation of the hydrocarbyl complexes cleanly results in formation of mixed valence Cu I Cu II complexes with varying degrees of distortion in both the bridging moiety and the dicopper core. Higher oxidation states, e.g. , dicopper(II), are easily accessed via oxidation of a dicopper(I) compound with air to give a Cu II 2 (μ-OH) 2 complex. Reduction of this compound with silanes resulted in the unexpected formation of pentametallic copper(I) dihydride clusters or trimetallic monohydride complexes, depending on the nature of the silane. Finally, development of an unsymmetrical naphthyridine ligand with mixed donor side-arms enables selective synthesis of an isostructural series of six heterobimetallic complexes, demonstrating the power of ligand design in the preparation of heterometallic assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Potential and spin-exchange interaction between Anderson impurities in graphene

The effective interaction between resonant magnetic Anderson impurities in graphene, mediated by conduction electrons, is studied as a function of the strength of the on-site energy level of the impurities and the amplitude of coupling to conduction electrons. Here, the sign and character of the interaction depend on whether the impurities reside on the same or opposite sublattices. For the same (opposite) sublattice, the potential interaction is attractive (repulsive) in the weak coupling limit with 1/R 3 dependence on the distance; the interaction reverses sign and becomes repulsive (attractive) in the strong coupling limit and displays 1/R behavior. The spin-exchange coupling is ferromagnetic (antiferromagnetic) at both large and small distances, but reverses sign and becomes antiferromagnetic (ferromagnetic) for intermediate distances. For opposite sublattices, the effective spin-exchange coupling is resonantly enhanced at distances where the energy levels cross the Dirac points.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A new approach to approximate equation-of-motion coupled cluster with triple excitations

Accurate methods for excited, ionized, and electron-attached states are critical to the study of many chemical species such as reactive intermediates, radicals, and ionized systems. The equation-of-motion coupled cluster singles, doubles, and triples (EOM-CCSDT) family of methods is very accurate (roughly similar in accuracy as for CCSDT calculations of the ground state), but the computational cost scales iteratively as the eighth power of the system size. Many approximations already exist, although most either correct only the excited state or require an iterative $\mathscr{O}$(n 7 ) procedure which can also be prohibitively expensive. In this paper, new methods, termed EOM-CCSD(T)(a) and EOM-CCSD(T)(a)*, are proposed which correct both the ground and excited states based on a shared effective Hamiltonian, and the latter of which includes only non-iterative corrections to both the CCSD and EOM-CCSD energies. These methods are found to significantly improve the description of excited and ionized potential energy surfaces, equilibrium geometries, and harmonic frequencies; the accuracy is very close to that of full EOM-CCSDT.

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

Framework-Topology-Controlled Singlet Fission in Metal–Organic Frameworks

Singlet fission (SF) has been explored as a viable route to improve photovoltaic performance by producing more excitons. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super exchange to generate triplet pairs. However, strongly coupled chromophores often form excimers that can serve as an SF intermediate or a low-energy trap site. The succeeding decoherence process, however, requires an optimum electronic coupling to facilitate the isolation of triplet production from the initially prepared correlated triplet pair. Conformational flexibility and dielectric modulation can provide a means to tune the SF mechanism and efficiency by modulating the interchromophoric electronic interaction. Such a strategy cannot be easily adopted in densely stacked traditional organic solids. Here, we show that the assembly of the SF-active chromophores around well-defined pores of solution-stable metal-organic frameworks (MOFs) can be a great platform for a modular SF process. A series of three new MOFs, built out from 9,10-bis(ethynylenephenyl)anthracene-derived struts, show a topology-defined packing density and conformational flexibility of the anthracene core to dictate the SF mechanism. Various steady-state and transient spectroscopic data suggest that the initially prepared singlet population can prefer either an excimer-mediated SF or a direct SF (both through a virtual charge-transfer (CT) state). Finally, these solution-stable frameworks offer the tunability of the dielectric environment to facilitate the SF process by stabilizing the CT state. Given that MOFs are a great platform for various photophysical and photochemical developments, generating a large population of long-lived triplets can expand their utilities in various photon energy conversion schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

An Overview of the EGS Collab Project: Field Validation of Coupled Process Modeling of Fracturing and Fluid Flow at the Sanford Underground Research Facility, Lead, SD

Enhanced Geothermal Systems (EGS) development will require an ability to accurately predict the flow rates and temperatures of the production wells. While simple in concept, complex heterogeneous fracture pathways can lead to channeling, short-circuiting, and premature thermal breakthrough complicating EGS. The EGS Collab project will establish a suite of intermediate-scale (~10-20 m) field test beds coupled with stimulation and interwell flow tests to provide a basis to better understand the fracture geometries and processes that control heat transfer between rock and stimulated fractures. These experiments will provide a means of testing tools, codes, and concepts that could later be employed under geothermal reservoir conditions at FORGE and in EGS. We will perform well-controlled, in situ experiments focused on rock fracture behavior and permeability enhancement. Pre- and post-test modeling of each test will allow for model prediction and validation. Comprehensive instrumentation will be used to collect high-quality, high-resolution geophysical and fracture characterization and fluid flow data. ,These data will be analyzed and compared with models and field observations to further elucidate the basic relationships between stress, induced seismicity, and permeability enhancement. To the maximum extent achievable, we will observe and quantify other key governing parameters that impact permeability, and attempt to understand how these parameters might change throughout the development and operation of an EGS project with the goal of enabling commercial viability of EGS. The Sanford Underground Research Facility (SURF) in South Dakota was selected as the EGS Collab project experimental site based on the evaluation of information from several sites. Our team has designed and constructed the first field experiment planned for this project, which is supported by the US Department of Energy’s Geothermal Technologies Office.

EGS, FORGE, field fracture stimulation and flow ex↗
DOE OSTI2019

Diesel Engine Waste Heat Driven Absorption Heat Pumps for ECU Applications in Defense Installations

A thermally activated absorption heat pump suitable for use in naval expeditionary Environmental Control Units, as well as residential space-conditioning, is developed. Waste heat characteristic of the exhaust stream from a diesel engine GenSet is used to drive an absorption cycle to provide cooling. The heat source is coupled to the heat pump using an intermediate fluid loop for flexible deployment. With minor modifications, the heat pump could also provide heating at high coefficients of performance, resulting in versatile functionality. This technology capitalizes on heat and mass transfer enhancement possible in microscale passages to provide a compact architecture for the components and the overall system. The working fluid pair with zero Global Warming Potential is contained within this assembly, reducing fluid inventories significantly over conventional systems. Quiet, reliable, long-life operation due to the absence of a compressor and the use of few moving parts are further critical distinguishing advantages. Modularity in cooling capacity has been demonstrated through scaling-up of component geometry and internal features and dimensions. The core technology was initially demonstrated with a proof-of-concept microscale absorption chiller measuring 200 × 200 × 34 mm and weighing 7 kg that delivered 300 W of cooling in laboratory tests. In the previous BEETIT project, the team made significant advances over the proof-of-concept. System and component designs with > 10× scale-up in capacity were developed, in a packaged unit capable of standalone operation with a semi-autonomous control system. A cooling capacity of 3.5 kW with a COP > 0.5 at an ambient temperature of 35°C was demonstrated for this natural gas-fired unit. Significant cost reductions in fabrication were achieved using low-cost brazing instead of diffusion bonding. In companion projects funded by the Southern Company and the Georgia Research Alliance, stamping and fluid forming techniques were investigated to fabricate microscale features instead of photochemical etching, thereby leading to significant cost reductions. In a follow-on effort funded by ARPA-E and NAVFAC, a 2.7 kW cooling unit was developed to provide cooling at a severe ambient condition of 51.7°C. The unit was driven directly by diesel engine exhaust heat. Innovative finned heat and mass exchangers for the ambient-coupled condenser and absorber were developed. In the present effort, a standalone, packaged and controllable 10.5 kW cooling capacity absorption chiller is developed. This demonstrates a 30× scale up from the proof-of-concept, thus validating the scalability of microchannel heat exchangers for absorption heat pumps. Autonomous operation algorithms demonstrated enhanced dynamic performance. The knowledge from previous projects was leveraged to develop novel component designs that further helped in miniaturizing the heat exchangers. All coupling fluids are hydronically coupled to aid flexible field deployment. The prototype unit provides design cooling capacity at high ambient temperature conditions of 44°C at COP > 0.6.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2016

Dense Chern-Simons matter with fermions at large N

In this paper we investigate properties of Chern-Simons theory coupled to massive fermions in the large N limit. We demonstrate that at low temperatures the system is in a Fermi liquid state whose features can be systematically compared to the standard phenomenological theory of Landau Fermi liquids. This includes matching microscopically derived Landau parameters with thermodynamic predictions of Landau Fermi liquid theory. We also calculate the exact conductivity and viscosity tensors at zero temperature and finite chemical potential. In particular we point out that the Hall conductivity of an interacting system is not entirely accounted for by the Berry flux through the Fermi sphere. Furthermore, investigation of the thermodynamics in the non-relativistic limit reveals novel phenomena at strong coupling. Furthermore, as the ’t Hooft coupling λ approaches 1, the system exhibits an extended intermediate temperature regime in which the thermodynamics is described by neither the quantum Fermi liquid theory nor the classical ideal gas law. Instead, it can be interpreted as a weakly coupled quantum Bose gas.

1/N Expansion↗
DOE OSTI2017

LHC signals from cascade decays of warped vector resonances

Recently (arXiv:1608.00526), a new framework for warped higher-dimensional compactifications with “bulk” standard model (SM) was proposed: in addition to the UV (Planck scale) and IR (a couple of TeV) branes, there is an intermediate brane, taken to be around 10TeV. The SM matter and Higgs fields propagate from the UV brane down to this intermediate brane only, while gauge and gravity fields propagate in the entire bulk. Such a configuration renders the lightest gauge Kaluza-Klein (KK) states within LHC reach, simultaneously satisfying flavor and CP constraints. In addition, the usual leading decay modes of the lightest KK gauge bosons into top and Higgs bosons are suppressed. This effect permits erstwhile subdominant channels to become significant. These include flavor-universal decays to SM fermions and Higgs bosons, and a novel channel — decay to a radion and a SM gauge boson, followed by radion decay to a pair of SM gauge bosons. In this work, we first delineate the parameter space where the above mentioned cascade decay of gauge KK particles dominates, and thereby can be the discovery mode at the LHC. We then perform a detailed analysis of the LHC signals from this model, finding that 300/fb suffices for evidence of KK-gluon in tri-jet, jet + di-photon and jet + di-boson channels. However, KK photon in photon + di-jet, and KK-W in leptonic W + di-jet require 3000/fb. The crucial feature of this decay chain is a “double” resonance, i.e. 3-particle and 2-particle invariant mass peaks, corresponding to the KK gauge boson and the radion respectively.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Lactate Racemase Nickel-Pincer Cofactor Operates by a Proton-Coupled Hydride Transfer Mechanism

Lactate racemase (LarA) of Lactobacillus plantarum contains a novel organometallic cofactor with nickel coordinated to a covalently tethered pincer ligand, pyridinium-3-thioamide-5-thiocarboxylic acid mononucleotide, but its function in the enzyme mechanism has not been elucidated. This study presents direct evidence that the nickel-pincer cofactor facilitates a proton-coupled hydride transfer (PCHT) mechanism during LarA-catalyzed lactate racemization. No signal was detected by electron paramagnetic resonance spectroscopy for LarA in the absence or presence of substrate, consistent with a +2 metal oxidation state and inconsistent with a previously proposed proton-coupled electron transfer mechanism. Pyruvate, the predicted intermediate for a PCHT mechanism, was observed in quenched solutions of LarA. A normal substrate kinetic isotope effect (k H /k D of 3.11 ± 0.17) was established using 2-α- 2 H-lactate, further supporting a PCHT mechanism. UV–visible spectroscopy revealed a lactate-induced perturbation of the cofactor spectrum, notably increasing the absorbance at 340 nm, and demonstrated an interaction of the cofactor with the inhibitor sulfite. Here, a crystal structure of LarA provided greater resolution (2.4 Å) than previously reported and revealed sulfite binding to the pyridinium C4 atom of the reduced pincer cofactor, mimicking hydride reduction during a PCHT catalytic cycle. Finally, computational modeling supports hydride transfer to the cofactor at the C4 position or to the nickel atom, but with formation of a nickel-hydride species requiring dissociation of the His200 metal ligand. In aggregate, these studies provide compelling evidence that the nickel-pincer cofactor acts by a PCHT mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Metallopolymerization as a Strategy to Translate Ligand-Modulated Chemoselectivity to Porous Catalysts

Porous catalysts have garnered substantial interest as potential platforms for group-transfer catalysis due to the ability to noncovalently colocalize substrates in proximity to site-isolated reactive intermediates. In contrast to soluble molecular catalysts, the limited synthetic toolbox available to prepare porous catalysts presents a formidable challenge to controlling the primary coordination sphere of lattice-confined catalysts and thus modulating the electronic structures of reactive catalyst intermediates. Here, we utilize Sonogashira cross-coupling chemistry to prepare a family of porous metallopolymers in the primary coordination sphere of Ru 2 sites. The newly synthesized materials are characterized by IR, elemental analysis, gas sorption, powder X-ray diffraction, thermogravimetric analysis, X-ray absorption spectroscopy, and diffuse-reflectance UV–vis-NIR spectroscopy. The resulting porous materials are catalysts for nitrene-transfer chemistry, and the chemoselectivity for allylic amination versus olefin aziridination can be tuned by modulating the primary coordination sphere of the catalyst sites. Furthermore, the demonstration of metallopolymerization as a rational synthetic strategy enables ligand-modulated chemoselectivity to be achieved with porous catalysts and represents a new opportunity to tailor the functionality of heterogeneous catalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗