Terminal Hydride Complex of High-Spin Mn.

The iron-molybdenum cofactor of nitrogenase (FeMoco) catalyzes fixation of N2 via Fe hydride intermediates. Our understanding of these species has relied heavily on the characterization of well-defined 3d metal hydride complexes, which serve as putative spectroscopic models. Although the Fe ions in FeMoco, a weak-field cluster, are expected to adopt locally high-spin Fe2+/3+ configurations, synthetically accessible hydride complexes featuring d5 or d6 electron counts are almost exclusively low-spin. We report herein the isolation of a terminal hydride complex of four-coordinate, high-spin (d5; S = 5/2) Mn2+. Electron paramagnetic resonance and electron-nuclear double resonance studies reveal an unusually large degree of spin density on the hydrido ligand. In light of the isoelectronic relationship between Mn2+ and Fe3+, our results are expected to inform our understanding of the valence electronic structures of reactive hydride intermediates derived from FeMoco.

Low-Coordinate Iron Hydride Chemistry at an N,N,C-Heteroscorpionate Platform.

Locally high-spin iron hydrides are proposed to play a critical role as intermediates in iron-molybdenum cofactor (FeMoco)-catalyzed N2 fixation. Inspired by these biological systems, we report herein our initial investigations into low-coordinate iron hydride chemistry supported by our N,N,C-heteroscorpionate ligands. Those ligands with smaller steric profiles are unable to completely suppress the formation of a binuclear [Fe(µ2-H)]2 complex; however, the incorporation of more substantial steric bulk allows for the isolation of a rare example of a terminal, high-spin (S = 2) Fe2+ hydride. Fourier transform infrared spectroscopy suggests an unusually weak Fe-H bond in the latter molecule. Mössbauer spectroscopies, coupled with density functional theory calculations, highlights the substantial influence of the terminal hydride ligand on 57Fe isomer shift.

Characterization by ENDOR Spectroscopy of the Iron-Alkyl Bond in a Synthetic Counterpart of Organometallic Intermediates in Radical SAM Enzymes.

Members of the radical S-adenosyl-l-methionine (SAM) enzyme superfamily initiate a broad spectrum of radical transformations through reductive cleavage of SAM by a [4Fe-4S]1+ cluster it coordinates to generate the reactive 5'-deoxyadenosyl radical (5'-dAdo•). However, 5'-dAdo• is not directly liberated for reaction and instead binds to the unique Fe of the cluster to create the catalytically competent S = 1/2 organometallic intermediate Ω. An alternative mode of reductive SAM cleavage, especially seen photochemically, instead liberates CH3•, which forms the analogous S = 1/2 organometallic intermediate with an Fe-CH3 bond, ΩM. The presence of a covalent Fe-C bond in both structures was established by the ENDOR observation of 13C and 1H hyperfine couplings to the alkyl groups that show isotropic components indicative of Fe-C bond covalency. The synthetic [Fe4S4]3+-CH3 cluster, M-CH3, is a crystallographically characterized analogue to ΩM that exhibits the same [Fe4S4]3+ cluster state as Ω and ΩM, and thus an analysis of its spectroscopic properties─and comparison with those of Ω and ΩM─can be grounded in its crystal structure. We report cryogenic (2 K) EPR and 13C/1/2H ENDOR measurements on isotopically labeled M-CH3. At low temperatures, the complex exhibits EPR spectra from two distinct conformers/subpopulations. ENDOR shows that at 2 K, one contains a static methyl, but in the other, the methyl undergoes rapid tunneling/hopping rotation about the Fe-CH3 bond. This generates an averaged hyperfine coupling tensor whose analysis requires an extended treatment of rotational averaging. The methyl group 13C/1/2H hyperfine couplings are compared with the corresponding values for Ω and ΩM.

The Pursuit of Perphenylterphenyls.

Tetradecaphenyl-p-terphenyl (2) was synthesized from 2,3,5,6-tetraphenyl-1,4-diiodobenzene (11) by two methods. Ullmann coupling of 11 with pentaphenyliodobenzene (9) gave compound 2 in 1.7 % yield, and Sonogashira coupling of 11 with phenylacetylene, followed by a double Diels-Alder reaction of the product diyne 12 with tetracyclone (6), gave 2 in 1.5 % overall yield. The latter reaction also gave the monoaddition product 4-(phenylethynyl)-2,2',3,3',4',5,5',6,6'-nonaphenylbiphenyl (13) in 4 % overall yield. The X-ray structures of compounds 2 and 13 show them to possess core aromatic rings distorted into shallow boat conformations. Density functional calculations indicate that these unusual structures are not the lowest energy conformations in the gas phase and may be the result of packing forces in the crystal. In addition, while uncorrected DFT calculations indicate that the strain energy in compound 2 is approximately 50 kcal/mol, dispersion-corrected DFT calculations suggest that it is essentially unstrained, due to compensating, favorable, intramolecular interactions of its many phenyl rings. An attempted synthesis of tetradecaphenyl-o-terphenyl (4) by reaction of diphenylhexatriyne (14) with three equivalents of tetracyclone at 350 °C gave only the diadduct 2-(phenylethynyl)-2',3,3',4,4',5,5',6,6'-nonaphenylbiphenyl (15) in 17 % yield. Even higher temperatures failed to produce 4 and lowered the yield of 15, perhaps due to rapid decomposition of the starting materials. Ullmann coupling of 3,4,5,6-tetraphenyl-1,2-diiodobenzene (16) and compound 9 also failed to give compound 4.

Four-Coordinate Fe N2 and Imido Complexes Supported by a Hemilabile NNC Heteroscorpionate Ligand.

Inspired by mechanistic proposals for N2 reduction at the nitrogenase FeMo cofactor, we report herein a new, strongly σ-donating heteroscorpionate ligand featuring two weak-field pyrazoles and an alkyl donor. This ligand supports four-coordinate Fe(I)-N2, Fe(II)-Cl, and Fe(III)-imido complexes, which we have characterized using a variety of spectroscopic and computational methods. Structural and quantum mechanical analysis reveal the nature of the Fe-C bonds to be essentially invariant between the complexes, with conversion between the (formally) low-valent Fe-N2 and high-valent Fe-imido complexes mediated by pyrazole hemilability. This presents a useful strategy for substrate reduction at such low-coordinate centers and suggests a mechanism by which FeMoco might accommodate the binding of both π-acidic and π-basic nitrogenous substrates.

An [Fe4S4]3+-Alkyl Cluster Stabilized by an Expanded Scorpionate Ligand.

Alkyl-ligated iron-sulfur clusters in the [Fe4S4]3+ charge state have been proposed as short-lived intermediates in a number of enzymatic reactions. To better understand the properties of these intermediates, we have prepared and characterized the first synthetic [Fe4S4]3+-alkyl cluster. Isolation of this highly reactive species was made possible by the development of an expanded scorpionate ligand suited to the encapsulation of cuboidal clusters. Like the proposed enzymatic intermediates, this synthetic [Fe4S4]3+-alkyl cluster adopts an S = 1/2 ground state with giso > 2. Mössbauer spectroscopic studies reveal that the alkylated Fe has an unusually low isomer shift, which reflects the highly covalent Fe-C bond and the localization of Fe3+ at the alkylated site in the solid state. Paramagnetic 1H NMR studies establish that this valence localization persists in solution at physiologically relevant temperatures, an effect that has not been observed for [Fe4S4]3+ clusters outside of a protein. These findings establish the unusual electronic-structure effects imparted by the strong-field alkyl ligand and lay the foundation for understanding the electronic structures of [Fe4S4]3+-alkyl intermediates in biology.

Assembly and Redox-Rich Hydride Chemistry of an Asymmetric Mo2S2 Platform.

Although molybdenum sulfide materials show promise as electrocatalysts for proton reduction, the hydrido species proposed as intermediates remain poorly characterized. We report herein the synthesis, reactions and spectroscopic properties of a molybdenum-hydride complex featuring an asymmetric Mo2S2 core. This molecule displays rich redox chemistry with electrochemical couples at E½ = -0.45, -0.78 and -1.99 V vs. Fc/Fc+. The corresponding hydrido-complexes for all three redox levels were isolated and characterized crystallographically. Through an analysis of solid-state bond metrics and DFT calculations, we show that the electron-transfer processes for the two more positive couples are centered predominantly on the pyridinediimine supporting ligand, whereas for the most negative couple electron-transfer is mostly Mo-localized.

Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes.

A series of thorium(IV)-imido complexes was synthesized and characterized. Extensive experimental and computational comparisons with the isostructural cerium(IV)-imido complexes revealed a notably more covalent bonding arrangement for the Ce═N bond compared with the more ionic Th═N bond. The thorium-imido moieties were observed to be 3 orders of magnitude more basic than their cerium congeners. More generally, these results provide unique experimental evidence for the larger covalent character of 4f05d0 Ce(IV) multiple bonds compared to its 5f06d0 Th(IV) actinide congener.

Functional Synthetic Model for the Lanthanide-Dependent Quinoid Alcohol Dehydrogenase Active Site.

The oxidation of methanol by dehydrogenase enzymes is an essential part of the bacterial methane metabolism cycle. The recent discovery of a lanthanide (Ln) cation in the active site of the XoxF dehydrogenase represents the only example of a rare-earth element in a physiological role. Herein, we report the first synthetic, functional model of Ln-dependent dehydrogenase and its stoichiometric and catalytic dehydrogenation of a benzyl alcohol. Density functional theory calculations implicate a hydride transfer mechanism for these reactions.

Understanding and Controlling the Emission Brightness and Color of Molecular Cerium Luminophores.

Molecular cerium complexes are a new class of tunable and energy-efficient visible- and UV-luminophores. Understanding and controlling the emission brightness and color are important for tailoring them for new and specialized applications. Herein, we describe the experimental and computational analyses for series of tris(guanidinate) (1-8, Ce{(R2N)C(N iPr)2}3, R = alkyl, silyl, or phenyl groups), guanidinate-amide [GA, A = N(SiMe3)2, G = (Me3Si)2NC(N iPr)2], and guanidinate-aryloxide (GOAr, OAr = 2,6-di- tert-butylphenoxide) cerium(III) complexes to understand and develop predictive capabilities for their optical properties. Structural studies performed on complexes 1-8 revealed marked differences in the steric encumbrance around the cerium center induced by various guanidinate ligand backbone substituents, a property that was correlated to photoluminescent quantum yield. Computational studies revealed that consecutive replacements of the amide and aryloxide ligands by guanidinate ligand led to less nonradiative relaxation of bright excited states and smaller Stokes shifts. The results establish a comprehensive structure-luminescence model for molecular cerium(III) luminophores in terms of both quantum yields and colors. The results provide a clear basis for the design of tunable, molecular, cerium-based, luminescent materials.

Selective Synthesis of Site-Differentiated Fe4S4 and Fe6S6 Clusters.

Obtaining rational control over the structure and nuclearity of metalloclusters is an ongoing challenge in synthetic Fe-S cluster chemistry. We report a new family of tridentate imidazolin-2-imine ligands L(NImR)3 that can bind [Fe4S4]2+ or [Fe6S6]3+ clusters, depending on the steric profile of the ligand and the reaction stoichiometry. A high-yielding synthetic route to L(NImR)3 ligands (where R is the imidazolyl N substituents) from trianiline and 2-chloroimidazolium precursors is described. For L(NImMe)3 (tris(1,3,5-(3-( N, N-dimethyl-4,5-diphenylimidazolin-2-imino)phenylmethyl))benzene), metalation with 1 equiv of [Ph4P]2[Fe4S4Cl4] and 3 equiv of NaBPh4 furnishes a mixture of products, but adjusting the stoichiometry to 1.5 equiv of [Ph4P]2[Fe4S4Cl4] provides (L(NImMe)3)Fe6S6Cl6 in high yield. Formation of an [Fe6S6]3+ cluster using L(NImTol)3 (tris(1,3,5-(3-( N, N-bis(4-methylphenyl)-4,5-diphenylimidazolin-2-imino)phenylmethyl))benzene) is not observed; instead, the [Fe4S4]2+ cluster [(L(NImTol)3)(Fe4S4Cl)][BPh4] is cleanly generated when 1 equiv of [Ph4P]2[Fe4S4Cl4] is employed. The selectivity for cluster nuclearity is rationalized by the orientation of the imidazolyl rings whereby long N-imidazolyl substituents preclude formation of [Fe6S6]3+ clusters but not [Fe4S4]2+ clusters. Thus, the structure and nuclearity of L(NImR)3-bound Fe-S clusters may be selectively controlled through rational modification the ligand's substituents.

Copper and Silver Complexes of a Redox-Active Diphosphine-Diboraanthracene Ligand.

Redox-active ligands and Z-type acceptor ligands have emerged as promising strategies for promoting multielectron redox chemistry at transition-metal centers. Herein, we report the synthesis and characterization of copper and silver complexes of a diphosphine ligand featuring a diboraanthracene core (B2P2, 9,10-bis(2-(diisopropylphosphino)phenyl)-9,10-dihydroboranthrene) that is capable of serving as both a redox reservoir and a Z-type ligand. Metalation of B2P2 with CuX (X = Cl, Br, I) results in the formation of bimetallic complexes of the formula (B2P2)Cu2X2 of two different structure types, depending on the halide. The Cu(I) cation [Cu(B2P2)]+ can be accessed by direct metalation of B2P2 with [Cu(CH3CN)4][PF6] or by halide abstraction with Na[BArF4] (ArF = 3,5-bis(trifluoromethyl)phenyl) with concomitant expulsion of CuX from the bimetallic Cu2X2 complexes. Metalation of B2P2 with AgCl results in the formation of the zwitterion Ag(B2P2)Cl featuring a diphosphine Ag cation tethered to a chloroborate anion. Metathesis of chloride for the noncoordinating [BArF4]- affords the cation [Ag(B2P2)]+. The cations [Cu(B2P2)]+ and [Ag(B2P2)]+ exhibit quasireversible reduction events at ∼ -1.6 V versus the ferrocene/ferrocenium redox couple, and the thermally sensitive radicals that result from their reduction, Cu(B2P2) and Ag(B2P2), were characterized by EPR spectroscopy and, in the case of the latter, single-crystal X-ray diffraction. Electronic structure calculations suggest these neutral radicals are best described as zwitterions with reduction centered at the diboraanthracene core.

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure.

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N- tert-butyl- N-(pyridin-2-yl)hydroxylamine (pyNO-). Electrochemical studies performed on the homoleptic complexes [M(pyNO)4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The salt [U(pyNO)4]+ was isolated by chemical oxidation of [U(pyNO)4]; spectroscopic and computational data support assignment as a UV cation.

N-Heterocyclic Carbene-Stabilized Boranthrene as a Metal-Free Platform for the Activation of Small Molecules.

The multielectron reduction of small molecules (e.g., CO2) is a key aspect of fuel synthesis from renewable electricity. Transition metals have been researched extensively in this role due to their intrinsic redox properties and reactivity, but more recently, strategies that forego transition metal ions for p-block elements have emerged. In this vein, we report an analogue of boranthrene (9,10-diboraanthracene) stabilized by N-heterocyclic carbenes and its one- and two-electron oxidized congeners. This platform exhibits reversible, two-electron redox chemistry at mild potentials and reacts with O2, CO2, and ethylene via formal [4+2] cycloaddition to the central diborabutadiene core. In an area traditionally dominated by transition metals, these results outline an approach for the redox activation of small molecules at mild potentials based on conjugated, light element scaffolds.

A Molecular Boroauride: A Donor-Acceptor Complex of Anionic Gold.

Gold is unique among the transition metals in that it is stable as an isolated anion (auride). Despite this fact, the coordination chemistry of anionic gold is virtually nonexistent, and this unique oxidation state is not readily exploited in conventional solution chemistry owing to its high reactivity. Through the use of a new molecular scaffold based on diboraanthracene (B2 P2 , 1), we have overcome these issues by avoiding the intermediacy of zerovalent gold and stabilizing the highly reduced gold anion through acceptor interactions. We have thus synthesized a molecular boroauride [(B2 P2 )Au]- ([2]- ) and showed its reversible conversion between Au-I and AuI states. Through a combination of spectroscopic and computational studies, we show the neutral state to be a AuI complex with a ligand radical anion. Bonding analyses (NBO and QTAIM) and the isolobal relationship between gold and hydrogen provide support for the description of [2]- as a boroauride complex.

A Terminal N2 Complex of High-Spin Iron(I) in a Weak, Trigonal Ligand Field.

The role of Fe in biological and industrial N2 fixation has inspired the intense study of small molecule analogues of Fe-(NxHy) intermediates of potential relevance to these processes. Although a number of low-coordinate Fe-(N2) featuring varying degrees of fidelity to the nitrogenase active site are now known, these complexes frequently feature strongly donating ligands that either enforce low- or intermediate-spin states or result in linear Fe-(N2)-Fe bridging motifs. Given that the nitrogenase active site uses weak-field sulfide ligands to stabilize its reactive Fe center(s), N2 binding to high-spin Fe is of great interest. Herein, we report the synthesis and characterization of the first terminal N2 complex of high-spin (S = 3/2) Fe(I) as well as a bridging Fe-(N2)-Fe analogue. Electron paramagnetic resonance and solution magnetic moment determination confirm the high-spin state, and vibrational experiments indicate a substantial degree of activation of the N≡N bond in these complexes. Density functional theory calculations reveal an electronic structure for the terminal adduct featuring substantial delocalization of unpaired spin onto the N2 ligand.

Bio-inspired transition metal-organic hydride conjugates for catalysis of transfer hydrogenation: experiment and theory.

Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI(+) ) organic hydride-acceptor domain has been coupled with a 1,10-phenanthroline (phen) metal-binding domain to afford a novel multifunctional ligand (L(BI+) ) with hydride-carrier capacity (L(BI+) +H(-) ⇌L(BI) H). Complexes of the type [Cp*M(L(BI) )Cl][PF6 ]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir(III) congener, X-ray crystallography. [Cp*Rh(L(BI) )Cl][PF6 ]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(L(BI) )Cl][PF6 ] and [Cp*M(phen)Cl][PF6 ] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate-driven RhH formation (90 kJ mol(-1) free-energy barrier), transfer of hydride between the Rh and BI(+) centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back-transfer of hydride from the BIH organic hydride donor to the Rh-activated imine substrate (89 kJ mol(-1) barrier), and exergonic protonation of the metal-bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.

An easy one-pot synthesis of diverse 2,5-di(2-pyridyl)pyrroles: a versatile entry point to metal complexes of functionalised, meridial and tridentate 2,5-di(2-pyridyl)pyrrolato ligands.

A wide variety of 2,5-di(2-pyridyl)pyrroles (dppHs) substituted at the C3 and C4 positions of the pyrrole core were obtained by direct condensation of a 2-pyridylcarboxaldehyde (2 equiv), an α-methylene ketone with at least one electron-withdrawing substituent and ammonium acetate. A novel 2,5-di(1,10-phenanthrolin-2-yl)pyrrole was also characterised. The dppHs provide a direct, quick entry to dipyridylpyrrolato (dpp(-) )-metal complexes. The meridial tridentate dpp(-) ligand is a useful anionic analogue of the terpyridyl ligand. The first (dpp)Ru complexes are described; the 3,4-substitution of the central pyrrole significantly perturbs the potentials of the redox processes of these complexes. A [(dpp)Ru(bpy)(MeCN)](+) (bpy=2,2'-bipyridine) complex is an electrocatalyst for the reductive disproportionation of carbon dioxide to carbon monoxide and the carbonate ion.

The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction.

In biological reduction processes the dihydronicotinamides NAD(P)H often transfer hydride to an unsaturated substrate bound within an enzyme active site. In many cases, metal ions in the active site bind, polarize and thereby activate the substrate to direct attack by hydride from NAD(P)H cofactor. This review looks more widely at the metal coordination chemistry of organic donors of hydride ion--organo-hydrides--such as dihydronicotinamides, other dihydropyridines including Hantzsch's ester and dihydroacridine derivatives, those derived from five-membered heterocycles including the benzimidazolines and benzoxazolines, and all-aliphatic hydride donors such as hexadiene and hexadienyl anion derivatives. The hydride donor properties--hydricities--of organo-hydrides and how these are affected by metal ions are discussed. The coordination chemistry of organo-hydrides is critically surveyed and the use of metal-organo-hydride systems in electrochemically-, photochemically- and chemically-driven reductions of unsaturated organic and inorganic (e.g. carbon dioxide) substrates is highlighted. The sustainable electrocatalytic, photochemical or chemical regeneration of organo-hydrides such as NAD(P)H, including for driving enzyme-catalysed reactions, is summarised and opportunities for development are indicated. Finally, new prospects are identified for metal-organo-hydride systems as catalysts for organic transformations involving 'hydride-borrowing' and for sustainable multi-electron reductions of unsaturated organic and inorganic substrates directly driven by electricity or light or by renewable reductants such as formate/formic acid.