Iodanyl Radical Catalysis.

ConspectusHypervalent iodine reagents find application as selective chemical oxidants in a diverse array of oxidative transformations. The utility of these reagents is often ascribed to (1) the proclivity to engage being selective two-electron redox transformations; (2) facile ligand exchange at the three-centered, four-electron (3c-4e) hypervalent iodine-ligand (I-X) bonds; and (3) the hypernucleofugacity of aryl iodides. One-electron redox and iodine radical chemistry is well-precedented in the context of inorganic hypervalent iodine chemistry─for example, in the iodide-triiodide couple that drives dye-sensitized solar cells. In contrast, organic hypervalent iodine chemistry has historically been dominated by the two-electron I(I)/I(III) and I(III)/I(V) redox couples, which results from intrinsic instability of the intervening odd-electron species. Transient iodanyl radicals (i.e., formally I(II) species), generated by reductive activation of hypervalent I-X bonds, have recently gained attention as potential intermediates in hypervalent iodine chemistry. Importantly, these open-shell intermediates are typically generated by activation of stoichiometric hypervalent iodine reagents, and the role of the iodanyl radical in substrate functionalization and catalysis is largely unknown.Our group has been interested in advancing the chemistry of iodanyl radicals as intermediates in the sustainable synthesis of hypervalent I(III) and I(V) compounds and as novel platforms for substrate activation at open-shell main-group intermediates. In 2018, we disclosed the first example of aerobic hypervalent iodine catalysis by intercepting reactive intermediates in aldehyde autoxidation chemistry. While we initially hypothesized that the observed oxidation was accomplished by aerobically generated peracids via a two-electron I(I)-to-I(III) oxidation reaction, detailed mechanistic studies revealed the critical role of acetate-stabilized iodanyl radical intermediates. We subsequently leveraged these mechanistic insights to develop hypervalent iodine electrocatalysis. Our studies resulted in the identification of new catalyst design principles that give rise to highly efficient organoiodide electrocatalysts that operate at modest applied potentials. These advances addressed classical challenges in hypervalent iodine electrocatalysis related to the need for high applied potentials and high catalyst loadings. In some cases, we were able to isolate the anodically generated iodanyl radical intermediates, which allowed direct interrogation of the elementary chemical reactions characteristic of iodanyl radicals. Both substrate activation via bidirectional proton-coupled electron transfer (PCET) reactions at I(II) intermediates and disproportionation reactions of I(II) species to generate I(III) compounds have been experimentally validated.This Account discusses the emerging synthetic and catalytic chemistry of iodanyl radicals. Results from our group have demonstrated that these open-shell species can play a critical role in sustainable synthesis of hypervalent iodine reagents and play a heretofore unappreciated role in catalysis. Realization of I(I)/I(II) catalytic cycles as a mechanistic alternative to canonical two-electron iodine redox chemistry promises to open new avenues to application of organoiodides in catalysis.

ß-Phenethylamine Synthesis: N-Pyridinium Aziridines as Latent Dual Electrophiles.

ß-Phenethylamines are widely represented in biologically and pharmacologically active organic small molecules. Here, we introduce N-pyridinium aziridines as latent dual electrophiles for the synthesis of ß-phenethylamines. Bromide-promoted ring opening generates ß-halopyridinium amines. Selective Ni-catalyzed C-C cross-coupling between organozinc nucleophiles and the benzylic C-Br electrophile affords a diverse family of ß-functionalized phenethylaminopyridinium salts, and coupling is stereoconvergent in the presence of chiral ligands. Subsequent Ni-catalyzed reductive N-N bond activation within the ß-functionalized phenethylaminopyridinium salts furnishes the products of formal olefin carboamination. Other reductive N-N cleavage reactions are demonstrated to provide access to free primary amines, alkylated amines, heterocycles, and products derived from N-centered radical chemistry. The developed reaction sequence can be implemented in the context of complex molecules and natural product derivatives. Together, the described results provide a general and modular synthesis of ß-phenethylamines and significantly expand the utility of N-pyridinium aziridines as linchpins in chemical synthesis.

Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films.

Synthetic porous materials continue to garner attention as platforms for solid-state chemistry and as designer heterogeneous catalysts. Applications in photochemistry and photocatalysis, however, are plagued by poor light harvesting efficiency due to light scattering resulting from sample microcrystallinity and poor optical penetration that arises from inner filter effects. Here we demonstrate the layer-by-layer growth of optically transparent, photochemically active thin films of porous salts. Films are grown by sequential deposition of cationic Zr-based porous coordination cages and anionic Mn porphyrins. Photolysis facilitates the efficient reduction of Mn(III) sites to Mn(II) sites, which can be observed in real-time by transmission UV-vis spectroscopy. Film porosity enables substrate access to the Mn(II) sites and facilitates reversible O2 activation in the solid state. These results establish optically transparent, porous salt thin films as versatile platforms for solid-state photochemistry and in operando spectroscopy.

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate.

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host-guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru2 nitride intermediate confined within the interstices of a Ru2-based metal-organic framework (MOF), Ru3(btc)2X3 (btc = 1,3,5-benzenetricarboxylate, i.e., Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C-H functionalization of benzylic C-H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues. Detailed study of the kinetic isotope effects (KIEs, i.e., kH/kD) of C-H amination, assayed both as intramolecular effects using partially labeled toluene and as intermolecular effects using a mixture of per-labeled and unlabeled toluene, provided evidence for restricted substrate mobility on the time scale of interstitial NAT. Analysis of these KIEs as a function of material mesoporosity provided approximate experimental values for functionalization in the absence of mass transport barriers. Here, we disclose a combined experimental and computational investigation of the mechanism of NAT from a Ru2 nitride to the C-H bond of toluene. Computed kinetic isotope effects for a H-atom abstraction (HAA)/radical rebound (RR) mechanism are in good agreement with experimental data obtained for C-H amination at the rapid diffusion limit. These results provide the first detailed analysis of the mechanism of intermolecular NAT to a C-H bond, bolster the use of KIEs as a probe of confinement effects on NAT within MOF lattices, and provide mechanistic insights unavailable by experiment because rate-determining mass transport obscured the underlying chemical kinetics.

Development of Nonclassical Photoprecursors for Rh2 Nitrenes.

Characterization of reactive intermediates in C-H functionalization is challenging due to the fleeting lifetimes of these species. Synthetic photochemistry provides a strategy to generate post-turnover-limiting-step intermediates in catalysis under cryogenic conditions that enable characterization. We have a long-standing interest in the structure and reactivity of Rh2 nitrene intermediates, which are implicated as transient intermediates in Rh2-catalyzed C-H amination. Previously, we demonstrated that Rh2 complexes bearing organic azide ligands can serve as solid-state and in crystallo photoprecursors in the synthesis of transient Rh2 nitrenoids. Complementary solution-phase experiments have not been available due to the weak binding of most organic azides to Rh2 complexes. Furthermore, the volatility of the N2 that is evolved during in crystallo nitrene synthesis from these precursors has prevented the in crystallo observation of C-H functionalization from lattice-confined nitrenes. Motivated by these challenges, here we describe the synthesis and photochemistry of nonclassical nitrene precursors based on sulfilimine ligands. Sulfilimines bind to Rh2 carboxylate complexes more tightly than the corresponding azides, which has enabled the full solid-state and solution-phase characterization of these new complexes. The higher binding affinity of sulfilimine ligands as compared with organic azides has enabled both solution-phase and solid-state nitrene photochemistry. Cryogenic photochemical studies of Rh2 sulfilimine complexes confined within polystyrene thin films demonstrate that sulfilimine photochemistry can be accomplished at low temperature but that C-H amination is rapid at temperatures compatible with N═S photoactivation. The potential of these structures to serve as platforms for multistep in crystallo cascades is discussed.

Ag(III)···Ag(III) Argentophilic Interaction in a Cofacial Corrole Dyad.

Metallophilic interactions between closed-shell metal centers are exemplified by d10 ions, with Au(I) aurophilic interactions as the archetype. Such an interaction extends to d8 species, and examples involving Au(III) are prevalent. Conversely, Ag(III) argentophilic interactions are uncommon. Here, we identify argentophilic interactions in silver corroles, which are authentic Ag(III) species. The crystal structure of a monomeric silver corrole is a dimer in the solid state, and the macrocycle exhibits an atypical domed conformation. In order to evaluate whether this represents an authentic metallophilic interaction or a crystal-packing artifact, the analogous cofacial or "pacman" corrole was prepared. The conformation of the monomer was recapitulated in the silver pacman corrole, exhibiting a short 3.67 Å distance between metal centers and a significant compression of the xanthene backbone. Theoretical calculations support the presence of a rare Ag(III)···Ag(III) argentophilic interaction in the pacman complex.

Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes.

Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of CuI complexes with N-heterocyclic diazoolefin ligands. The complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.

Iodine-Iodine Cooperation Enables Metal-Free C-N Bond-Forming Electrocatalysis via Isolable Iodanyl Radicals.

Small molecule redox mediators convey interfacial electron transfer events into bulk solution and can enable diverse substrate activation mechanisms in synthetic electrocatalysis. Here, we report that 1,2-diiodo-4,5-dimethoxybenzene is an efficient electrocatalyst for C-H/E-H coupling that operates at as low as 0.5 mol % catalyst loading. Spectroscopic, crystallographic, and computational results indicate a critical role for a three-electron I-I bonding interaction in stabilizing an iodanyl radical intermediate (i.e., formally I(II) species). As a result, the optimized catalyst operates at more than 100 mV lower potential than the related monoiodide catalyst 4-iodoanisole, which results in improved product yield, higher Faradaic efficiency, and expanded substrate scope. The isolated iodanyl radical is chemically competent in C-N bond formation. These results represent the first examples of substrate functionalization at a well-defined I(II) derivative and bona fide iodanyl radical catalysis and demonstrate one-electron pathways as a mechanistic alternative to canonical two-electron hypervalent iodine mechanisms. The observation establishes I-I redox cooperation as a new design concept for the development of metal-free redox mediators.

C-H Activation of Inert Arenes using a Photochemically Activated Guanidinato-Magnesium(I) Compound.

UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg}2 ] 3 (Priso=[(DipN)2 CNPri 2 ]- , Dip=2,6-diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C-H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg}2 (µ-H)(µ-Ar)] 4-9. In contrast to similar reactions reported for ß-diketiminate coordinated counterparts of 3, these C-H activations proceed with little regioselectivity, though they are considerably faster. Reaction of 3 with an excess of the pyridine, p-NC5 H4 But (pyBut ), gave [(Priso)Mg(pyBut H)(pyBut )2 ] 10, presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(pyBut ⋅)(pyBut )2 ] 11, which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C-H activations. One of these involves photochemical cleavage of the Mg-Mg bond of 3, generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give "Birch-like" products, which subsequently rearrange via C-H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of 3 leads to an intramolecular aliphatic C-H activation process and formation of an alkyl-bridged magnesium(II) species, [{Mg(µ-Priso-H )}2 ] 12. Furthermore, irradiation of a 1 : 1 mixture of 3 and the ß-diketiminato dimagnesium(I) compound, [{(Dip Nacnac)Mg}2 ] (Dip Nacnac=[HC(MeCNDip)2 ]- ), effects a "scrambling" reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg-Mg(Dip Nacnac)] 13. Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated 3 is dominated by a broad featureless signal, indicating the presence of a doublet radical species.

Traceless Benzylic C-H Amination via Bifunctional N-Aminopyridinium Intermediates.

C-H amination reactions provide the opportunity to streamline the synthesis of nitrogen-containing organic small molecules. The impact of intermolecular C-H amination methods, however, is currently limited the frequent requirement for the amine precursors to bear activating groups, such as N-sulfonyl substituents, that are both challenging to remove and not useful synthetic handles for subsequent derivatization. Here, we introduce traceless nitrogen activation for C-H amination-which enables application of selective C-H amination chemistry to the preparation of diverse N-functionalized products-via sequential benzylic C-H N-aminopyridylation followed by Ni-catalyzed C-N cross-coupling with aryl boronic acids. Unlike many C-H amination reactions that provide access to protected amines, the current method installs an easily diversifiable synthetic handle that serves as a lynchpin for C-H amination, deaminative N-N functionalization sequences.

Nitrogen Atom Transfer Catalysis by Metallonitrene C-H Insertion: Photocatalytic Amidation of Aldehydes.

C-H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C-H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd-N) with a diradical nitrogen ligand that is singly bonded to PdII . Despite the subvalent nitrene character, selective C-H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3 SiMe3 . Based on these results, a photocatalytic protocol for aldehyde C-H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C-H nitrogen atom transfer offers facile access to primary amides after deprotection.

Cis-Divacant Octahedral Fe(II) in a Dimensionally Reduced Family of 2-(Pyridin-2-yl)pyrrolide Complexes.

Four-coordinate transition-metal complexes can adopt a diverse array of coordination geometries, with square planar and tetrahedral coordination being the most prevalent. Previously, we reported the synthesis of a trinuclear Fe(II) complex, Fe3TPM2, supported by a 3-fold-symmetric 2-pyridylpyrrolide ligand [i.e., tris(5-(pyridin-2-yl)-1H-pyrrol-2-yl)methane] that featured a rare cis-divacant octahedral (CDO) geometry at each Fe(II) center. Here, a series of truncated 2-pyridylpyrrolide ligands are described that support mono- and binuclear Fe(II) complexes that also exhibit CDO geometries. Metalation of the tetradentate ligand bis[5-(pyridin-2-yl)-1H-pyrrol-2-yl]methane (H2BPM) in tetrahydrofuran (THF) results in the binuclear complex Fe2(BPM)2(THF)2 in which both Fe(II) ions are octahedrally coordinated. The coordinated THF solvent ligands are labile: THF dissociation leads to Fe2(BPM)2, which features five-coordinate Fe(II) ions. The Fe-Fe distance in these binuclear complexes can be elongated by ligand methylation. Metalation of bis[5-(6-methylpyridin-2-yl)-1H-pyrrol-2-yl]methane (H2BPMMe) in THF leads to the formation of four-coordinate, CDO Fe(II) centers in Fe(BPMMe)2. Further ligand truncation affords bidentate ligands 2-(1H-pyrrol-2-yl)pyridine (PyrPyrrH) and 2-methyl-6-(1H-pyrrol-2-yl)pyridine (PyrMePyrrH). Metalation of these ligands in THF affords six-coordinate complexes Fe(PyrPyrr)2(THF)2 and Fe(PyrMePyrr)2(THF)2. Dissociation of labile solvent ligands provides access to four-coordinate Fe(II) complexes. Ligand disproportionation at Fe(PyrPyrr)2 results in the formation of Fe(PyrPyrr)3 and Fe(0). Ligand methylation suppresses this disproportionation and enables isolation of Fe(PyrMePyrr)2, which is rigorously CDO. Complete ligand truncation, by separating the 2-pyridylpyrrolide ligands into the constituent monodentate pyridyl and pyrrolide donors, affords Fe(Pyr)2(Pyrr)2 in which Fe(II) is tetrahedrally coordinated. Computational analysis indicates that the potential energy surface that dictates the coordination geometry in this family of four-coordinate complexes is fairly flat in the vicinity of CDO coordination. These synthetic studies provide the structural basis to explore the implications of CDO geometry on Fe-catalyzed reactions.

Electronic Structure Analysis and Reactivity of the Bimetallic Bis-Titanocene Vinylcarboxylate Complex, [(Cp2Ti)2(O2C3TMS2)]†.

Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp2Ti)2(O2C3TMS2)] has been revisited with EPR, confirming a predominantly TiIII/TiIII electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic TiIII center remained unperturbed, with reactions taking place at the pendent κ2(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.

Nitrene Photochemistry of Manganese N-Haloamides*.

Manganese complexes supported by macrocyclic tetrapyrrole ligands represent an important platform for nitrene transfer catalysis and have been applied to both C-H amination and olefin aziridination catalysis. The reactivity of the transient high-valent Mn nitrenoids that mediate these processes renders characterization of these species challenging. Here we report the synthesis and nitrene transfer photochemistry of a family of MnIII N-haloamide complexes. The S=2 N-haloamide complexes are characterized by 1 H NMR, UV-vis, IR, high-frequency and -field EPR (HFEPR) spectroscopies, and single-crystal X-ray diffraction. Photolysis of these complexes results in the formal transfer of a nitrene equivalent to both C-H bonds, such as the α-C-H bonds of tetrahydrofuran, and olefinic substrates, such as styrene, to afford aminated and aziridinated products, respectively. Low-temperature spectroscopy and analysis of kinetic isotope effects for C-H amination indicate halogen-dependent photoreactivity: Photolysis of N-chloroamides proceeds via initial cleavage of the Mn-N bond to generate MnII and amidyl radical intermediates; in contrast, photolysis of N-iodoamides proceeds via N-I cleavage to generate a MnIV nitrenoid (i.e., {MnNR}7 species). These results establish N-haloamide ligands as viable precursors in the photosynthesis of metal nitrenes and highlight the power of ligand design to provide access to reactive intermediates in group-transfer catalysis.

Electrocatalytic C-N Coupling via Anodically Generated Hypervalent Iodine Intermediates.

Development of new electrosynthetic chemistry promises to impact the efficiency and sustainability of organic synthesis. Here we demonstrate that anodically generated hypervalent iodine intermediates effectively couple interfacial electron transfer with oxidative C-H/N-H coupling chemistry. The developed hypervalent iodine electrocatalysis is applicable in both intra- and intermolecular C-N bond-forming reactions. Available mechanistic data indicate that anodic oxidation of aryl iodides generates a transient I(II) intermediate that is critically stabilized by added acetate ions. This report represents the first example of metal-free hypervalent iodine electrocatalysis for C-H functionalization and provides mechanistic insight that we anticipate will contribute to the development of hypervalent iodine mediators for synthetic electrochemistry.

C-H Amination Mediated by Cobalt Organoazide Adducts and the Corresponding Cobalt Nitrenoid Intermediates.

Treatment of (ArL)CoBr (ArL = 5-mesityl-1,9-(2,4,6-Ph3C6H2)dipyrrin) with a stoichiometric amount of 1-azido-4-(tert-butyl)benzene N3(C6H4-p-tBu) furnished the corresponding four-coordinate organoazide-bound complex (ArL)CoBr(N3(C6H4-p-tBu)). Spectroscopic and structural characterization of the complex indicated redox innocent ligation of the organoazide. Slow expulsion of dinitrogen (N2) was observed at room temperature to afford a ligand functionalized product via a [3 + 2] annulation, which can be mediated by a high-valent nitrene intermediate such as a CoIII iminyl (ArL)CoBr(•N(C6H4-p-tBu)) or CoIV imido (ArL)CoBr(N(C6H4-p-tBu)) complex. The presence of the proposed intermediate and its viability as a nitrene group transfer reagent are supported by intermolecular C-H amination and aziridination reactivities. Unlike (ArL)CoBr(N3(C6H4-p-tBu)), a series of alkyl azide-bound CoII analogues expel N2 only above 60 °C, affording paramagnetic intermediates that convert to the corresponding Co-imine complexes via α-H-atom abstraction. The corresponding N2-released structures were observed via single-crystal-to-crystal transformation, suggesting formation of a Co-nitrenoid intermediate in solid-state. Alternatively, the alkyl azide-bound congeners supported by a more sterically accessible dipyrrinato scaffold tBuL (tBuL = 5-mesityl-(1,9-di-tert-butyl)dipyrrin) facilitate intramolecular 1,3-dipolar cycloaddition as well as C-H amination to furnish 1,2,3-dihydrotriazole and substituted pyrrolidine products, respectively. For the C-H amination, we observe that the temperature required for azide activation varies depending on the presence of weak C-H bonds, suggesting that the alkyl azide adducts serve as viable species for C-H amination when the C-H bonds are (1) proximal to the azide moiety and (2) sufficiently weak to be activated.

In Crystallo Snapshots of Rh2-Catalyzed C-H Amination.

While X-ray crystallography routinely provides structural characterization of kinetically stable pre-catalysts and intermediates, elucidation of the structures of transient reactive intermediates, which are intimately engaged in bond-breaking and -making during catalysis, is generally not possible. Here, we demonstrate in crystallo synthesis of Rh2 nitrenoids that participate in catalytic C-H amination, and we characterize these transient intermediates as triplet adducts of Rh2. Further, we observe the impact of coordinating substrate, which is present in excess during catalysis, on the structure of transient Rh2 nitrenoids. By providing structural characterization of authentic C-H functionalization intermediates, and not kinetically stabilized model complexes, these experiments provide the opportunity to define critical structure-activity relationships.

Dual Polymerization Pathway for Polyolefin-Polar Block Copolymer Synthesis via MILRad: Mechanism and Scope.

This work explores the mechanism whereby a cationic diimine Pd(II) complex combines coordination insertion and radical polymerization to form polyolefin-polar block copolymers. The initial requirement involves the insertion of a single acrylate monomer into the Pd(II)-polyolefin intermediates, which generate a stable polymeric chelate through a chain-walking mechanism. This thermodynamically stable chelate was also found to be photochemically inactive, and a unique mechanism was discovered which allows for radical polymerization. Rate-determining opening of the chelate by an ancillary ligand followed by additional chain walking allows the metal to migrate to the α-carbon of the acrylate moiety. Ultimately, the molecular parameters necessary for blue-light-triggered Pd-C bond homolysis from this α-carbon to form a carbon-centered macroradical species were established. This intermediate is understood to initiate free radical polymerization of acrylic monomers, thereby facilitating block copolymer synthesis from a single Pd(II) complex. Key intermediates were isolated and comprehensively characterized through exhaustive analytical methods which detail the mechanism while confirming the structural integrity of the polyolefin-polar blocks. Chain walking combined with blue-light irradiation functions as the mechanistic switch from coordination insertion to radical polymerization. On the basis of these discoveries, robust di- and triblock copolymer syntheses have been demonstrated with olefins (ethylene and 1-hexene) which produce amorphous or crystalline blocks and acrylics (methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate) in broad molecular weight ranges and compositions, yielding AB diblocks and BAB triblocks.

Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization.

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal-organic frameworks (MOFs) is now achieved by polymerization of molecular Ru2 [II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)2 . The resulting crystalline heterobimetallic MOFs are solid solutions of Ru2 and Cu2 sites housed within [M3 L2 ] phases. The developed mechanochemical strategy is modular and allows for systematic control of the primary coordination sphere of the Ru2 sites within an isoreticular family of materials. This strategy is anticipated to provide a rational approach to atomically precise mixed-metal materials.

Measuring and Modulating Substrate Confinement during Nitrogen-Atom Transfer in a Ru2-Based Metal-Organic Framework.

The porosity and synthetic tunability of metal-organic frameworks (MOFs) has motivated interest in application of these materials as designer heterogeneous catalysts. While understanding substrate mobility in these materials is critical to the rational development of highly active catalyst platforms, experimental data are rarely available. Here we demonstrate kinetic isotope effect (KIE) analysis enables direct evaluation of the extent of substrate confinement as a function of material mesoporosity. Further, we provide evidence that suggests substrate confinement within a microporous Ru2-based MOF gives rise to quantum tunneling during interstitial C-H amination. The reported data provide the first evidence for tunneling during interstitial MOF chemistry and illustrate an experimental strategy to evaluate the impact of material structure on substrate mobility in porous catalysts.