A discrete, dicopper μ-alkynyl complex, [Cu₂(μ-η¹:η¹-C≡C(C₆H₄)CH₃)DPFN]NTf₂ (DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine; NTf₂^- = N(SO₂CF₃)₂^-), reacts with p-tolylazide to yield a dicopper complex with a symmetrically bridging 1,2,3-triazolide, [Cu₂(μ-η¹:η¹-(1,4-bis(4-tolyl)-1,2,3-triazolide))DPFN]NTf₂. This transformation exhibits bimolecular reaction kinetics and represents a key step in a proposed, bimetallic mechanism for copper-catalyzed azide-alkyne cycloaddition (CuAAC). The μ-alkynyl and μ-triazolide complexes undergo reversible redox events (by cyclic voltammetry), suggesting that a cycloaddition pathway involving mixed-valence dicopper species might also be possible. Synthesis and characterization of the mixed-valence μ-alkynyl dicopper complex, [Cu₂(μ-η¹:η¹-C≡C(C₆H₄)CH₃)DPFN](NTf₂)₂, revealed an electronic structure with an unexpected partially delocalized spin, as evidenced by electron paramagnetic resonance spectroscopy. Studies of the mixed-valence μ-alkynyl complex's reactivity suggest that a mixed-valence pathway is less likely than one involving intermediates with only copper(I).

A strong σ-donating cyclic (alkyl)(amino) carbene (cAAC) triggers rearrangement of the silyl(aryl) amido ligand -N(SiMe₃)Dipp (Dipp = 2,6-diisopropylphenyl) in the coordination sphere of titanium(III) to afford a novel zwitterionic titanium imido complex with a TiCH₂SiMe₂[cAAC] linkage. Reduction of this species produces a new DippN=Ti imido complex containing a cAAC-centered radical species, characterized by single crystal diffraction analysis and electron paramagnetic resonance spectroscopy.

Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high-yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X-ray crystallography) of PAHs containing one or more appended dienes with the ortho-quinodimethane (o-QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels-Alder reactions.

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 Cu^ICu^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^II₂(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.

A dicopper complex featuring a symmetrically bridging nitrile ligand and supported by a binucleating naphthyridine-based ligand, [Cu₂(μ-η ¹ :η ¹ -MeCN)DPFN](NTf₂)₂, was treated with phosphaalkynes (RC[triple bond, length as m-dash]P, isoelectronic analogues of nitriles) to yield dicopper complexes that exhibit phosphaalkynes in rare μ-η ²:η ² binding coordination modes. X-ray crystallography revealed that these unusual "tilted" structures exist in two isomeric forms (R "up" vs. R "sideways"), depending on the steric profile of the phosphaalkyne's alkyl group (R = Me, Ad, or ^t Bu). Only one isomer is observed in both solution and the solid state for R = Me (sideways) and ^t Bu (up). With intermediate steric bulk (R = Ad), the energy difference between the two geometries is small enough that both are observed in solution, and NMR spectroscopy and computations indicate that the solid-state structure corresponds to the minor isomer observed in solution. Meanwhile, treatment of [Cu₂(μ-η ¹:η ¹-MeCN)DPFN](NTf₂)₂ with 2-butyne affords [Cu₂(μ-η ²:η ²-(MeC[triple bond, length as m-dash]CMe))DPFN](NTf₂)₂: its similar ligand geometry demonstrates that the tilted μ-η ²:η ² binding mode is not limited to phosphaalkynes but reflects a more general trend, which can be rationalized via an NBO analysis showing maximization of π-backbonding.

The oxo-cobalt cubane unit [Co₄O₄] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co₄O₄] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [CoIII4O₄]⁴⁺/[CoIII3Co^IVO₄]⁵⁺ and [CoIII3Co^IVO₄]⁵⁺/[CoIII2CoIV2O₄]⁶⁺ redox potentials are reliably predicted by the pK_as of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ∼500 mV. The potential-pK_a correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure-reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.

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.

Incorporation of Mn into an established water oxidation catalyst based on a Co(III)₄O₄ cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo₃O₄(OAc)₅py₃ (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc^- ligand for Cl^- (1-Cl), NO₃^- (1-NO₃), and pyridine ([1-py]⁺). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [Mn^IVCo^III₃]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo₃O₄ cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.