Metal-Metal Redox Exchange to Produce Heterometallic Manganese-Cobalt Oxo Cubanes via a "Dangler" Intermediate.

Pendent metals bound to heterocubanes are components of well-known active sites in enzymes that mediate difficult chemical transformations. Investigations into the specific role of these metal ions, sometimes referred to as "danglers", have been hindered by a paucity of rational synthetic routes to appropriate model structures. To generate pendent metal ions bonded to an oxo cubane through a carboxylate bridge, the cubane Co4(µ3-O)4(OAc)4(t-Bupy)4 (OAc = acetate, t-Bupy = 4-tert-butylpyridine) was exposed to various metal acetate complexes. Reaction with Cu(OAc)2 gave the structurally characterized (by X-ray diffraction) dicopper dangler Cu2Co4(µ4-O)2(µ3-O)2(OAc)6(Cl)2(t-Bupy)4. In contrast, the analogous reaction with Mn(OAc)2 produced the MnIV-containing cubane cation [MnCo3(µ3-O)4(OAc)4(t-Bupy)4]+ by way of a metal-metal exchange that gives Co(OAc)2 and [CoIII(µ-OH)(OAc)]n oligomers as byproducts. Additionally, reaction of the formally CoIV cubane complex [Co4(µ3-O)4(OAc)4(t-Bupy)4][PF6] with Mn(OAc)2 gave the corresponding Mn-containing cubane in 80% yield. A mechanistic examination of the related metal-metal exchange reaction between Co4(µ3-O)4(OBz)4(py)4 (OBz = benzoate) and [Mn(acac)2(py)2][PF6] by ultraviolet-visible (UV-vis) spectroscopy provided support for a process involving rate-determining association of the reactants and electron transfer through a µ-oxo bridge in the adduct intermediate. The rates of exchange correlate with the donor strength of the cubane pyridine and benzoate ligand substituents; more electron-donating pyridine ligands accelerate metal-metal exchange, while both electron-donating and -withdrawing benzoate ligands can accelerate exchange. These experiments suggest that the basicity of the cubane oxo ligands promotes metal-metal exchange reactivity. The redox potentials of the Mn and cubane starting materials and isotopic labeling studies suggest an inner-sphere electron-transfer mechanism in a dangler intermediate.

A Ruthenophosphanorcaradiene as a Synthon for an Ambiphilic Metallophosphinidene.

Reaction of the ruthenium carbene complex Cp*(IPr)RuCl (1) (IPr = 1,3-bis(Dipp)imidazol-2-ylidene; Dipp = 2,6-diisopropylphenyl) with sodium phosphaethynolate (NaOCP) led to intramolecular dearomatization of one of the Dipp substituents on the Ru-bound carbene to afford a Ru-bound phosphanorcaradiene, 2. Computations by DFT reveal a transition state characterized by a concerted process whereby CO migrates to the Ru center as the P atom adds to the π system of the aryl group. The phosphanorcaradiene possesses ambiphilic properties and reacts with both nucleophilic and electrophilic substrates, resulting in rearomatization of the ligand aryl group with net P atom transfer to give several unusual metal-bound, P-containing main-group moieties. These new complexes include a metallo-1-phospha-3-azaallene (Ru─P═C═NR), a metalloiminophosphanide (Ru─P═N─R), and a metallophosphaformazan (Ru─P(═N─N═CPh2)2). Reaction of 2 with the carbene 2,3,4,5-tetramethylimidazol-2-ylidene (IMe4) produced the corresponding phosphaalkene DippP═IMe4.

A [CoSiH2] Silylene Synthon Provides Modular Access to Homo- and Heterobimetallic [Co═Si═M] (M = Co, Fe) Silicide Complexes.

Base-stabilized [BP3iPr](H)2CoSiH2(DMAP) (1, [BP3iPr] = PhB(CH2PiPr2)3-; DMAP = 4-dimethylaminopyridine) is a rare instance of a synthon for the simplest "parent" silylene complex (LM═SiH2). Complex 1 was accessed in high yields via double Si-H bond activation in SiH4 by [BP3iPr]Co(DMAP), and in solution, it undergoes rapid exchange between bound and free DMAP by an associative mechanism (as determined by variable-temperature 1H NMR dynamic studies). The DMAP ligand of 1 is readily displaced by metal-based fragments that bind silicon and cleave the Si-H bonds of the SiH2 moiety to produce bimetallic [Co═Si═M] (M = Co, Fe) molecular silicides. Thus, treatment of 1 with 0.5 equiv of (LCoI)2(µ-N2) (L = a tripodal ligand) resulted in the spontaneous formation of [BP3iPr](H)2Co═Si═Co(H)2L (L = [BP2tBuPz], PhB(CH2PtBu2)2(pyrazolyl)- (3); Tp″, HB(3,5-diisopropylpyrazolyl)3- (4)) with the concomitant release of DMAP. The symmetrical silicide [BP3iPr](H)2Co═Si═Co(H)2[BP3iPr] (5) was prepared by treatment of a mixture of 1 and [BP3iPr]Co(DMAP) with 2 equiv of Ph3B, which in this case is required to sequester DMAP as the elimination product Ph3B-DMAP. A heterobimetallic silicide, [BP3iPr](H)2Co═Si═Fe(H)2[SiP3iPr] (7; [SiP3iPr] = PhSi(CH2PiPr2)3), was obtained via in situ KC8 reduction of [SiP3iPr]FeCl and subsequent addition of 1 and Ph3B. These transformations involving a metal-SiH2 derivative demonstrate a fundamentally new type of reactivity for silylene complexes and provide a unique synthetic method for construction of molecular silicide complexes.

Direct Transformation of SiH4 to a Molecular L(H)2Co═Si═Co(H)2L Silicide Complex.

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si-H bond activations in SiH4 at the metal centers of 14-electron LCoI fragments (L = Tp″, HB(3,5-diisopropylpyrazolyl)3-; [BP2tBuPz], PhB(CH2PtBu2)2(pyrazolyl)). Upon exposure of (Tp″Co)2(µ-N2) (1) to SiH4, a mixture of (Tp″Co)2(µ-H) (2) and (Tp″Co)2(µ-H)2 (3) was formed and no evidence for Si-H oxidative addition products was observed. In contrast, [BP2tBuPz]-supported Co complexes led to Si-H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP2tBuPz]Co)2(µ-N2) (5) with SiH4 gave the dicobalt silicide complex [BP2tBuPz](H)2Co═Si═Co(H)2[BP2tBuPz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. The effect of the [BP2tBuPz] ligand on Co-Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP2tBuPz]Co(L)x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH4, despite the lack of significant Si-H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of MexSiH4-x (x = 1-3), demonstrating functionalization of the µ-silicon atom in a molecular silicide to form organosilanes.

Dimetalloylene (M-E-M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E-X Bonds (X=N(SiMe3 )2 , OtBu) with an Iridium Hydride.

Reactions of the IrV hydride [Me BDIDipp ]IrH4 {BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6-iPr2 C6 H3 } with E[N(SiMe3 )2 ]2 (E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([Me BDIDipp ]IrH)2 (µ2 -E)2 in good yields. Moreover, ([Me BDIDipp ]IrH)2 (µ2 -Ge)2 was formed in situ from thermal decomposition of [Me BDIDipp ]Ir(H)2 Ge[N(SiMe3 )2 ]2 . These reactions are accompanied by liberation of HN(SiMe3 )2 and H2 through the apparent cleavage of an E-N(SiMe3 )2 bond by Ir-H. In a reversal of this process, ([Me BDIDipp ]IrH)2 (µ2 -E)2 reacted with excess H2 to regenerate [Me BDIDipp ]IrH4 . Varying the concentrations of reactants led to formation of the trimeric ([Me BDIDipp ]IrH2 )3 (µ2 -E)3 . The further scope of this synthetic route was investigated with group 15 amides, and ([Me BDIDipp ]IrH)2 (µ2 -Bi)2 was prepared by the reaction of [Me BDIDipp ]IrH4 with Bi(NMe2 )3 or Bi(OtBu)3 to afford the first example of a "naked" two-coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir2 E2 (E=Sn, Pb) compounds characterized them as open-shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir2 Bi2 is characterized as having a closed-shell singlet ground state.

Mechanistic Aspects of Cobalt-Oxo Cubane Clusters in Oxidation Chemistry.

Cobalt oxides are recognized as one of the most efficient earth-abundant catalysts for challenging oxidation chemistry, with substrates ranging from water to organic compounds. In these oxidations, cobalt-oxo species with formal oxidation states greater than 3 are commonly invoked as reactive intermediates. However, there is a dearth of mechanistic information regarding how these high-valent cobalt catalysts operate. This Perspective describes how the study of molecular cobalt oxo clusters, with an emphasis on [Co4O4] oxo cubane complexes, has helped to shed light on the operative mechanisms of cobalt-catalyzed oxidation reactions. Implications for high-valent CoIV-oxo and CoV-oxo intermediates and remaining mechanistic questions concerning how these intermediates mediate O-O bond formation are also discussed. Furthermore, structural modifications of these oxo cubane clusters (i.e., incorporation of heteroatoms and modulation of ligands) have provided insight into multimetallic cooperativity, but the influence of such metal-metal interactions on oxidation activity remains to be explored. A more detailed understanding of these structure-activity relationships may enable fine-tuning of reactivity and stability of synthetic multimetallic catalysts for energy storage and challenging organic transformations.

Versatile Fe-Sn Bonding Interactions in a Metallostannylene System: Multiple Bonding and C-H Bond Activation.

The metallostannylene Cp*(iPr2MeP)(H)2Fe-SnDMP (1; Cp* = η5-C5Me5; DMP = 2,6-dimesitylphenyl), formed by hydrogen migration in a putative Cp*(iPr2MeP)HFe[Sn(H)DMP] intermediate, serves as a robust platform for exploration of transition-metal main-group element bonding and reactivity. Upon one-electron oxidation, 1 expels H2 to generate the coordinatively unsaturated [Cp*(iPr2MeP)Fe═SnDMP][B(C6F5)4] (3), which possesses a highly polarized Fe-Sn multiple bond that involves interaction of the tin lone pair with iron. Evidence from EPR and 57Fe Mössbauer spectroscopy, along with DFT studies, shows that 3 is primarily an iron-based radical with charge localization at tin. Upon reduction of 3, C-H bond activation of the phosphine ligand was observed to produce Cp*HFe(κ2-(P,Sn)═Sn(DMP)CH2CHMePMeiPr) (5). Complex 5 was also accessed via thermolysis of 1, and kinetics studies of this thermolytic pathway indicate that the reductive elimination of H2 from 1 to produce a stannylyne intermediate, Cp*(iPr2MeP)Fe[SnDMP] (A), is likely rate-determining. Evidence indicates that the production of 5 proceeds through a concerted C-H bond activation. DFT investigations suggest that the transition state for this transformation involves C-H cleavage across the Fe-Sn bond and that a related transition state where C-H bond activation occurs exclusively at the tin center is disfavored, illustrating an effect of iron-tin cooperativity in this system.

Expanded [23]-Helicene with Exceptional Chiroptical Properties via an Iterative Ring-Fusion Strategy.

Expanded helicenes are an emerging class of helical nanocarbons composed of alternating linear and angularly fused rings, which give rise to an internal cavity and a large diameter. The latter is expected to impart exceptional chiroptical properties, but low enantiomerization free energy barriers (ΔG‡e) have largely precluded experimental interrogation of this prediction. Here, we report the syntheses of expanded helicenes containing 15, 19, and 23 rings on the inner helical circuit, using two iterations of an Ir-catalyzed, site-selective [2 + 2 + 2] reaction. This series of compounds displays a linear relationship between the number of rings and ΔG‡e. The expanded [23]-helicene, which is 7 rings longer than any known single carbohelicene and among the longest known all-carbon ladder oligomers, exhibits a ΔG‡e that is high enough (29.2 ± 0.1 kcal/mol at 100 °C in o-DCB) to halt enantiomerization at ambient temperature. This enabled the isolation of enantiopure samples displaying circular dichroism dissymmetry factors of ±0.056 at 428 nm, which are ≥1.7× larger than values for previously reported classical and expanded helicenes. Computational investigations suggest that this improved performance is the result of both the increased diameter and length of the [23]-helicene, providing guiding design principles for high dissymmetry molecular materials.

Copper(III) Metallacyclopentadienes via Zirconocene Transfer and Reductive Elimination to an Isolable Phenanthrocyclobutadiene.

Despite the widespread use of copper catalysis for the formation of C-C bonds, debate about the mechanism persists. Reductive elimination from Cu(III) is often invoked as a key step, yet examples of its direct observation from isolable complexes remain limited to only a few examples. Here, we demonstrate that incorporation of bulky mesityl (Mes) groups into the α-positions of a phenanthrene-appended zirconacyclopentadiene, Cp2Zr(2,5-Mes2-phenanthro[9,10]C4), enables efficient oxidative transmetalation to the corresponding, formal Cu(III) metallacyclopentadiene dimer. The dimer was quantitatively converted to a structurally analogous anionic monomer [nBu4N]{Cl2Cu(2,5-Mes2-phenanthro[9,10]C4)} upon treatment with [nBu4N][Cl]. Both metallacycles undergo quantitative reductive elimination upon heating to generate phenanthrocyclobutadiene and a Cu(I) species. Due to the steric protection provided by the mesityl groups, this cyclobutadiene was isolated and thoroughly characterized to reveal antiaromaticity comparable to that of free cyclobutadiene, which imbues it with a small highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap of 1.85 eV and accessible reduced and oxidized electronic states.

Stabilization of reactive Co4O4 cubane oxygen-evolution catalysts within porous frameworks.

A major challenge to the implementation of artificial photosynthesis (AP), in which fuels are produced from abundant materials (water and carbon dioxide) in an electrochemical cell through the action of sunlight, is the discovery of active, inexpensive, safe, and stable catalysts for the oxygen evolution reaction (OER). Multimetallic molecular catalysts, inspired by the natural photosynthetic enzyme, can provide important guidance for catalyst design, but the necessary mechanistic understanding has been elusive. In particular, fundamental transformations for reactive intermediates are difficult to observe, and well-defined molecular models of such species are highly prone to decomposition by intermolecular aggregation. Here, we present a general strategy for stabilization of the molecular cobalt-oxo cubane core (Co4O4) by immobilizing it as part of metal-organic frameworks, thus preventing intermolecular pathways of catalyst decomposition. These materials retain the OER activity and mechanism of the molecular Co4O4 analog yet demonstrate unprecedented long-term stability at pH 14. The organic linkers of the framework allow for chemical fine-tuning of activity and stability and, perhaps most importantly, provide "matrix isolation" that allows for observation and stabilization of intermediates in the water-splitting pathway.

A Dicopper Nitrenoid by Oxidation of a CuICuI Core: Synthesis, Electronic Structure, and Reactivity.

A dicopper nitrenoid complex was prepared by formal oxidative addition of the nitrenoid fragment to a dicopper(I) center by reaction with the iminoiodinane PhINTs (Ts = tosylate). This nitrenoid complex, (DPFN)Cu2(µ-NTs)[NTf2]2 (DPFN = 2,7-bis(fluorodi(2-pyridyl)methyl)-1,8-naphthyridine), is a powerful H atom abstractor that reacts with a range of strong C-H bonds to form a mixed-valence Cu(I)/Cu(II) µ-NHTs amido complex in the first example of a clean H atom transfer to a dicopper nitrenoid core. In line with this reactivity, DFT calculations reveal that the nitrenoid is best described as an iminyl (NR radical anion) complex. The nitrenoid was trapped by the addition of water to form a mixed-donor hydroxo/amido dicopper(II) complex, which was independently obtained by reaction of a Cu2(µ-OH)2 complex with an amine through a protonolysis pathway. This mixed-donor complex is an analogue for the proposed intermediate in copper-catalyzed Chan-Evans-Lam coupling, which proceeds via C-X (X = N or O) bond formation. Treatment of the dicopper(II) mixed donor complex with MgPh2(THF)2 resulted in generation of a mixture that includes both phenol and a previously reported dicopper(I) bridging phenyl complex, illustrating that both reduction of dicopper(II) to dicopper(I) and concomitant C-X bond formation are feasible.

C-H Activation by RuCo3O4 Oxo Cubanes: Effects of Oxyl Radical Character and Metal-Metal Cooperativity.

High-valent multimetallic-oxo/oxyl species have been implicated as intermediates in oxidative catalysis involving proton-coupled electron transfer (PCET) reactions, but the reactive nature of these oxo species has hindered the development of an in-depth understanding of their mechanisms and multimetallic character. The mechanism of C-H oxidation by previously reported RuCo3O4 cubane complexes bearing a terminal RuV-oxo ligand, with significant oxyl radical character, was investigated. The rate-determining step involves H atom abstraction (HAA) from an organic substrate to generate a Ru-OH species and a carbon-centered radical. Radical intermediates are subsequently trapped by another equivalent of the terminal oxo to afford isolable radical-trapped cubane complexes. Density functional theory (DFT) reveals a barrierless radical combination step that is more favorable than an oxygen-rebound mechanism by 12.3 kcal mol-1. This HAA reactivity to generate organic products is influenced by steric congestion and the C-H bond dissociation energy of the substrate. Tuning the electronic properties of the cubane (i.e., spin density localized on terminal oxo, basicity, and redox potential) by varying the donor ability of ligands at the Co sites modulates C-H activations by the RuV-oxo fragment and enables construction of structure-activity relationships. These results reveal a mechanistic pathway for C-H activation by high-valent metal-oxo species with oxyl radical character and provide insights into cooperative effects of multimetallic centers in tuning PCET reactivity.

Scalable, Divergent Synthesis of a High Aspect Ratio Carbon Nanobelt.

Carbon nanobelts are molecules of high fundamental and technological interest due to their structural similarity to carbon nanotubes, of which they are molecular cutouts. Despite this attention, synthetic accessibility is a major obstacle, such that the few known strategies offer limited structural diversity, functionality, and scalability. To address this bottleneck, we have developed a new strategy that utilizes highly fused monomer units constructed via a site-selective [2 + 2 + 2] cycloaddition and a high-yielding zirconocene-mediated macrocyclization to achieve the synthesis of a new carbon nanobelt on large scale with the introduction of functional handles in the penultimate step. This nanobelt represents a diagonal cross section of an armchair carbon nanotube and consequently has a longitudinally extended structure with an aspect ratio of 1.6, the highest of any reported nanobelt. This elongated structure promotes solid-state packing into aligned columns that mimic the parent carbon nanotube and facilitates unprecedented host-guest chemistry with oligo-arylene guests in nonpolar solvents.

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. 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 CuICuII 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 CuII2(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.

Siloxyaluminate and Siloxygallate Complexes as Models for Framework and Partially Hydrolyzed Framework Sites in Zeolites and Zeotypes.

Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu)3 ]4 - and HOM[OSi(OtBu)3 ]3 - (where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu)3 ]3 Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown-4 afforded charge-separated ion pairs composed of monomeric anions M[OSi(OtBu)3 ]4 - with outer-sphere [([12]crown-4)2 Li]+ cations, and hydroxides {HOM[OSi(OtBu)3 ]3 } with pendant [([12]crown-4)Li]+ cations. These molecular models were characterized by single-crystal X-ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown-4)Li]{HOM[OSi(OtBu)3 ]3 } complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin-Ponndorf-Verley (MPV) transfer hydrogenations with Al/Ga-doped silica catalysts.

Elucidation of Diverse Solid-State Packing in a Family of Electron-Deficient Expanded Helicenes via Microcrystal Electron Diffraction (MicroED)*.

Solid-state packing plays a defining role in the properties of a molecular organic material, but it is difficult to elucidate in the absence of single crystals that are suitable for X-ray diffraction. Herein, we demonstrate the coupling of divergent synthesis with microcrystal electron diffraction (MicroED) for rapid assessment of solid-state packing motifs, using a class of chiral nanocarbons-expanded helicenes-as a proof of concept. Two highly selective oxidative dearomatizations of a readily accessible helicene provided a divergent route to four electron-deficient analogues containing quinone or quinoxaline units. Crystallization efforts consistently yielded microcrystals that were unsuitable for single-crystal X-ray diffraction, but ideal for MicroED. This technique facilitated the elucidation of solid-state structures of all five compounds with <1.1 Šresolution. The otherwise-inaccessible data revealed a range of notable packing behaviors, including four different space groups, homochirality in a crystal for a helicene with an extremely low enantiomerization barrier, and nanometer scale cavities.

Mechanistic Interrogation of Alkyne Hydroarylations Catalyzed by Highly Reduced, Single-Component Cobalt Complexes.

Highly reactive catalysts for ortho-hydroarylations of alkynes have previously been reported to result from activation of CoBr2 by Grignard reagents, but the operative mechanism and identity of the active cobalt species have been undefined. A mechanistic analysis of a related system, involving hydroarylations of a (N-aryl)aryl ethanimine with diphenylacetylene, was performed using isolable reduced Co complexes. Studies of the stoichiometric reaction of Co(I) or Co(II) precursors with CyMgCl implicated catalyst initiation via a ß-H elimination/deprotonation pathway. The resulting single-component Co(-I) complex is proposed as the direct pre-catalyst. Michaelis-Menten enzyme kinetic studies provide mechanistic details regarding the catalytic dependence on substrate. The (N-aryl)aryl ethanimine substrate exhibited saturation-like behavior, whereas alkyne demonstrated a complex dependency; rate inhibition and promotion depend on the relative concentration of alkyne to imine. Activation of the aryl C-H bond occurred only in the presence of coordinated alkyne, which suggests operation of a concerted metalation-deprotonation (CMD) mechanism. Small primary isotope effects are consistent with a rate-determining C-H cleavage. Off-cycle olefin isomerization catalyzed by the same Co(-I) active species appears to be responsible for the observed Z-selectivity.

Shape-Selective Synthesis of Pentacene Macrocycles and the Effect of Geometry on Singlet Fission.

Pentacene's extraordinary photophysical and electronic properties are highly dependent on intermolecular through-space interactions. Macrocyclic arrangements of chromophores have been shown to provide a high level of control over these interactions, but few examples exist for pentacene due to inherent synthetic challenges. In this work, zirconocene-mediated alkyne coupling was used as a dynamic covalent C-C bond forming reaction to synthesize two geometrically distinct, pentacene-containing macrocycles on a gram scale and in four or fewer steps. Both macrocycles undergo singlet fission in solution with rates that differ by an order of magnitude, while the rate of triplet recombination is approximately the same. This independent modulation of singlet and triplet decay rates is highly desirable for the design of efficient singlet fission materials. The dimeric macrocycle adopts a columnar packing motif in the solid state with large void spaces between pentacene units of the crystal lattice.

Expanded Helicenes as Synthons for Chiral Macrocyclic Nanocarbons.

Expanded helicenes are large, structurally flexible π-frameworks that can be viewed as building blocks for more complex chiral nanocarbons. Here we report a gram-scale synthesis of an alkyne-functionalized expanded [11]helicene and its single-step transformation into two structurally and functionally distinct types of macrocyclic derivatives: (1) a figure-eight dimer via alkyne metathesis (also gram scale) and (2) two arylene-bridged expanded helicenes via Zr-mediated, formal [2+2+n] cycloadditions. The phenylene-bridged helicene displays a substantially higher enantiomerization barrier (22.1 kcal/mol) than its helicene precursor (<11.9 kcal/mol), which makes this a promising strategy to access configurationally stable expanded helicenes. In contrast, the topologically distinct figure-eight retains the configurational lability of the helicene precursor. Despite its lability in solution, this compound forms homochiral single crystals. Here, the configuration is stabilized by an intricate network of two distinct yet interconnected helical superstructures. The enantiomerization mechanisms for all new compounds were probed using density functional theory, providing insight into the flexibility of the figure-eight and guidance for future synthetic modifications in pursuit of non-racemic macrocycles.

Structure and Bonding in a Diamond-Shaped Tin Cluster Possessing a cyclo-Sn4 Core.

A tetrameric cluster composed entirely of (aryl)Sn units, [DMPSn]4 (DMP=2,6-dimesitylphenyl), has been prepared by reduction of [DMPSnCl]2 with a variety of reductants. This cluster was characterized in solution by multinuclear NMR spectroscopies, as well as in the solid-state by single crystal X-ray diffraction analysis. This species is stereochemically nonrigid in solution and possesses a cyclo-Sn4 core whose DMP substituents are equivalent at higher temperatures. The solid-state molecular structure is remarkably unsymmetrical and possesses a nearly planar cyclo-Sn4 core. The DMP substituents are arranged such that three are approximately coplanar, while one is nearly perpendicular to the cyclo-Sn4 core. Density functional theory calculations for a [PhSn]4 model system show that this distorted geometry about the cyclo-Sn4 core maximizes σ-bonding between the Sn centers in a manner reminiscent of trans-bent bonding in the heavy group 14 analogues of alkenes and alkynes.