Utilization of BODIPY-based redox events to manipulate the Lewis acidity of fluorescent boranes.

This report describes the implementation of a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye into the ligand framework of a borane. The redox-active nature of the BODIPY dye is utilized to generate a family of molecular boranes that are capable of exhibiting tunable Lewis acidities through BODIPY-based redox events.

Tuning the reduction potentials of benzoquinone through the coordination to Lewis acids.

Electron transfer promoted by the coordination of a substrate molecule to a Lewis acid or hydrogen bonding group is a critical step in many biological and catalytic transformations. This computational study investigates the nature of the interaction between benzoquinone and one and two Lewis acids by examining the influence of Lewis acid strength on the ability to alter the two reduction potentials of the coordinated benzoquinone molecule. To investigate this interaction, the coordination of the neutral (Q), singly reduced ([Q]˙-), and doubly reduced benzoquinone ([Q]2-) molecule to eight Lewis acids was analyzed. Coordination of benzoquinone to a Lewis acid became more favorable by 25 kcal mol-1 with each reduction of the benzoquinone fragment. Coordination of benzoquinone to a Lewis acid also shifted each of the reduction potentials of the coordinated benzoquinone anodically by 0.50 to 1.5 V, depending on the strength of the Lewis acid, with stronger Lewis acids exhibiting a larger effect on the reduction potential. Coordination of a second Lewis acid further altered each of the reduction potentials by an additional 0.70 to 1.6 V. Replacing one of the Lewis acids with a proton resulted in the ability to modify the pKa of the protonated Lewis acid-Q/[Q]˙-/[Q]2- adducts by about 10 pKa units, in addition to being able to alter the ability to transfer a hydrogen atom by 10 kcal mol-1, and the capacity to transfer a hydride by about 30 kcal mol-1.

Microwave-Assisted Synthesis of Zirconium Phosphate Nanoplatelet-Supported Ru-Anadem Nanostructures and Their Catalytic Study for the Hydrogenation of Acetophenone.

The catalytic hydrogenation of organic compounds containing carbonyl groups has been extensively studied and widely used in industrial processes. Herein, we report the preparation of a novel nanomaterial, α-zirconium phosphate (α-ZrP) nanoplatelet-supported ruthenium nano-anadem catalyst, which possesses high selectivity in the catalytic hydrogenation of aromatic ketones. The α-ZrP nanoplatelets were prepared using a modified reflux method. Through an ion-exchange and reduction reaction pathway, ruthenium nanoparticles were loaded on ZrP to produce Ru-ZrP with a nano-anadem structure. The successful synthesis of Ru-ZrP composites is supported by a series of characterization techniques (PXRD, SEM, TEM, EDS, XPS, FT-IR, etc.). Compared with pure ZrP nanoplatelets, the catalytic hydrogenation of acetophenone has been dramatically improved when using Ru-ZrP. Full conversion was achieved at room temperature, and the yield of 1-cyclohexylehtanol was up to 95%. The effects of reaction time, reaction temperature, and hydrogen pressure were investigated. The investigation illustrates that there are two proposed reaction pathways in the hydrogenation of acetophenone, which are further supported by computational analyses. Recycling experiments indicate that the Ru-ZrP material could be reused four times without a noticeable activity decrease.

Redox switchable catalysis utilizing a fluorescent dye.

This report describes the implementation of a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye into the ligand framework of a Rh-based catalyst. The redox-active nature of the BODIPY dye is utilized to generate a catalyst that is capable of exhibiting redox-switchable catalytic behavior for the hydroboration of alkenes through a BODIPY-based reduction.

Connecting Solution-Phase to Single-Molecule Properties of Ni(Salophen).

We present a strong correlation of the Ni(salophen) structure and properties measured in single-molecule vs bulk quantities and in ultra high vacuum vs solution phase. Under a scanning tunneling microscope (STM), Ni(salophen) forms a self-assembled monolayer (SAM) on Au(111) at 23 °C with molecular structure identical to that of the X-ray crystallographic measurement. The HOMO and LUMO levels are determined using elastic tunneling spectroscopy at the single-molecule level with confirmation by monolayer-quantity ultraviolet photoelectron spectroscopy (UPS) and by cyclic voltammetry (CV) measurements. The STM-determined HOMO-LUMO gap of 3.28 eV and (HOMO-1)-HOMO gap of 0.36 eV form a new foundation for the selection of hybrid functionals with a simple basis set to be effective in accurately calculating single-molecule Ni(salophen) frontier MO levels. Our results suggest that microscopy-based experiments on a surface, along with free-molecule gas-phase calculations, can provide useful insights into the physical properties of metal(salen) complexes, especially when such direct measurements are not available in solution.

Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction.

Catalysts for the oxidation of NH3 are critical for the utilization of NH3 as a large-scale energy carrier. Molecular catalysts capable of oxidizing NH3 to N2 are rare. This report describes the use of [Cp*Ru(PtBu 2 NPh 2 )(15 NH3 )][BArF 4 ], (PtBu 2 NPh 2 =1,5-di(phenylaza)-3,7-di(tert-butylphospha)cyclooctane; ArF =3,5-(CF3 )2 C6 H3 ), to catalytically oxidize NH3 to dinitrogen under ambient conditions. The cleavage of six N-H bonds and the formation of an N≡N bond was achieved by coupling H+ and e- transfers as net hydrogen atom abstraction (HAA) steps using the 2,4,6-tri-tert-butylphenoxyl radical (t Bu3 ArO. ) as the H atom acceptor. Employing an excess of t Bu3 ArO. under 1 atm of NH3 gas at 23 °C resulted in up to ten turnovers. Nitrogen isotopic (15 N) labeling studies provide initial mechanistic information suggesting a monometallic pathway during the N⋅⋅⋅N bond-forming step in the catalytic cycle.

Investigation of main group promoted carbon dioxide reduction.

The reduction of carbon dioxide (CO2) is of interest to the chemical industry, as many synthetic materials can be derived from CO2. To help determine the reagents needed for the functionalization of carbon dioxide this experimental and computational study describes the reduction of CO2 to formate and CO with hydride, electron, and proton sources in the presence of sterically bulky Lewis acids and bases. The insertion of carbon dioxide into a main group hydride, generating a main group formate, was computed to be more thermodynamically favorable for more hydridic (reducing) main group hydrides. A ten kcal/mol increase in hydricity (more reducing) of a main group hydride resulted in a 35% increase in the main group hydride's ability to insert CO2 into the main group hydride bond. The resulting main group formate exhibited a hydricity (reducing ability) about 10% less than the respective main group hydride prior to CO2 insertion. Coordination of a second identical Lewis acid to a main group formate complex further reduced the hydricity by about another 20%. The addition of electrons to the CO adduct of t Bu3P and B(C6F5)3 resulted in converting the sequestered CO2 molecule to CO. Reduction of the CO2 adduct of t Bu3P and B(C6F5)3 with both electrons and protons resulted in only proton reduction.

Synthesis and Characterization of Hydrazine-Appended BODIPY Dyes and the Related Aminomethyl Complexes.

The synthesis and characterization of three new organic hydrazines containing BODIPY dyes is described. The respective aminomethyl complexes were also synthesized to aid in the assignment of the physical properties that were hydrazine-based vs. BODIPY-based. Incorporation of a BODIPY dye into an organic hydrazine introduced a reduction event (average value of -1.70 V vs. Cp2Fe/Cp2Fe+). Although two irreversible oxidation events were observed, it was unclear whether the oxidation events arose from BODIPY-based or amine/hydrazine-based oxidations. The respective BODIPY-appended hydrazine complexes exhibited excited state lifetimes on the order of 2-6 ns, suggesting the presence of a singlet excited state. The excited state lifetimes of the BODIPY-appended hydrazine complexes were about a factor of ten greater than the respective aminomethyl complexes. Computational analysis showed that by appending a BODIPY dye to a hydrazine fragment the hydrazine fragment becomes more susceptible to transfer H2 equivalents as protons and hydrides as opposed to H-atoms, which occurs with common organic hydrazines. Computational analysis also revealed that the BODIPY-based redox events can be used to manipulate the mechanism for H2 transfer from the BODIPY-appended hydrazine, where a BODIPY-based reduction favors H-atom transfer and a BODIPY-based oxidation favors proton transfer followed by hydride transfer.

A new era for electron bifurcation.

Electron bifurcation, or the coupling of exergonic and endergonic oxidation-reduction reactions, was discovered by Peter Mitchell and provides an elegant mechanism to rationalize and understand the logic that underpins the Q cycle of the respiratory chain. Thought to be a unique reaction of respiratory complex III for nearly 40 years, about a decade ago Wolfgang Buckel and Rudolf Thauer discovered that flavin-based electron bifurcation is also an important component of anaerobic microbial metabolism. Their discovery spawned a surge of research activity, providing a basis to understand flavin-based bifurcation, forging fundamental parallels with Mitchell's Q cycle and leading to the proposal of metal-based bifurcating enzymes. New insights into the mechanism of electron bifurcation provide a foundation to establish the unifying principles and essential elements of this fascinating biochemical phenomenon.

Utilization of a Fluorescent Dye Molecule as a Proton and Electron Reservoir.

Fluorescent dyes have been widely utilized as chemical sensors and in photodynamic therapy, but exploitation of their redox-active nature in chemical reactions has remained mostly unexplored. This report describes the isolation of a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based radical. The redox-active nature of the BODIPY compound can be utilized in combination with a guanidine center, the basicity of which can be manipulated by greater than 14 pKa units, to promote the conversion of protons and electrons into H-atoms for transfer to substrate molecules.

Influence of Lewis acid strength on hydride transfer to unsaturated substrates.

Hydride transfer promoted by the coordination of a substrate molecule to a Lewis acid is a critical step in many catalytic transformations. This computational study investigates the nature of the interaction between a polar substrate molecule and a Lewis acid by examining the influence of Lewis acid strength on the ability to reduce (transfer a hydride to) the coordinated substrate molecule. To investigate this interaction, the coordination of 10 probe substrates to seven Lewis acids was analyzed. Coordination of the probe substrate molecules to a Lewis acid resulted in a more favorable reduction of the substrate molecule by 20-70 kcal mol-1. Further examination of the coordination of the substrate molecules to Lewis acids of varying Lewis acid strengths resulted in a direct linear correlation between the ability of the Lewis acid-substrate adduct to accept a hydride and the Lewis acid strength. The linear correlations also revealed that between 44 and 70% of the Lewis acidity of the Lewis acids translated to the Lewis acid-substrate adducts. From the results obtained in this study, the minimum Lewis acid strength needed to activate the substrates for the reduction with [BH4]- and the implications of employing a Lewis acid to promote the reduction of an unsaturated polar substrate in catalytic reactions are also described.

Influence of intramolecular vs. intermolecular phosphonium-borohydrides in catalytic hydrogen, hydride, and proton transfer reactions.

In this computational study, the thermodynamics of hydrogen, hydride, and proton transfer from 22 phosphonium-borohydride intramolecular and intermolecular frustrated Lewis pairs (FLPs) to eight probe substrates was investigated. The purpose of this study was to gain insight into the thermodynamics of H2 transfer with intramolecular phosphonium-borohydrides; to determine whether intramolecular or intermolecular FLPs are preferred in FLP-catalyzed hydrogenation reactions. Comparison of the computed thermodynamic values showed that by connecting a borohydride and phosphonium center through a linker, H2 loss from the respective intramolecular phosphonium-borohydride became less favorable by about five and seven kcal mol-1 in acetonitrile and toluene, respectively. Connecting the borohydride and phosphonium centers also resulted in both hydride and proton loss becoming less favorable, on average, by about 10.0 kcal mol-1 and about 4.6 pKa units, respectively. Analysis of hydrogen, proton, and hydride transfer to eight probe substrates showed that initial proton transfer is 49 and 20 kcal mol-1 more favorable than the initial hydride transfer in the reduction of nitrogen-containing and oxygen-containing unsaturated substrates, respectively. These results suggest that proton transfer, followed by hydride transfer occurs in the reduction of imines, ketones, aldehydes, and enamines. From the thermodynamic analysis of proton and hydride transfer, an intramolecular phosphonium-borohydride was the desired catalyst for the reduction of imines and enamines, while an intermolecular phosphonium-borohydride was the favored catalyst for the reduction of ketones and aldehydes.

Quantification of Lewis acid induced Brønsted acidity of protogenic Lewis bases.

Proton transfer promoted by the coordination of protogenic Lewis bases to a Lewis acid is a critical step in catalytic transformations. Although the acidification of water upon coordination to a Lewis acid has been known for decades, no attempts have been made to correlate the Brønsted acidity of the coordinated water molecule with Lewis acid strength. To probe this effect, the pKa's (estimated error of 1.3 pKa units) in acetonitrile of ten protogenic Lewis bases coordinated to seven Lewis acids containing Lewis acidities varying 70 kcal mol-1, were computed. To quantify Lewis acid strength, the ability to transfer a hydride (hydride donor ability) from the respective main group hydride was used. Coordination of a Lewis acid to water increased the acidity of the bound water molecule between 20 and 50 pKa units. A linear correlation exhibiting a 2.6 pKa unit change of the Lewis acid-water adduct per ten kcal mol-1 change in hydride donor ability of the respective main group hydride was obtained. For the ten protogenic Lewis bases studied, the coordinated protogenic Lewis bases were acidified between 10 and 50 pKa units. On average, a ten kcal mol-1 change in hydride donor ability of the respective main group hydride resulted in about a 2.8 pKa unit change in the Brønsted acidity of the Lewis acid-Lewis base adducts. Since attempts to computationally investigate the pKa of main group dihydrogen complexes were unsuccessful, experimental determination of the first reported pKa of a main group dihydrogen complex is described. The pKa of H2-B(C6F5)3 was determined to be 5.8 ± 0.2 in acetonitrile.

Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3 Complex.

We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH3]+ complex using the 2,4,6-tri-tert-butylphenoxyl radical to yield a Mo-alkylimido ([Mo═NR]+) complex (R = 2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one). Chemical reduction of [Mo═NR]+ generates a terminal Mo≡N nitride complex upon N-C bond cleavage, and a [Mo═NH]+ complex is formed by protonation of the nitride. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from [Mo-NH3]+ and formation of [Mo═NR]+.

Deconvoluting the Innocent vs. Non-innocent Behavior of N,N-diethylphenylazothioformamide Ligands with Copper Sources.

Redox-active ligands lead to ambiguity in often clearly defined oxidation states of both the metal centre and the ligand. The arylazothioformamide (ATF) ligand class represents a redox-active ligand with three possible redox states (neutral, singly reduced, and doubly reduced). ATF-metal interactions result in strong colorimetric transitions allowing for the use of ATFs in metal detection and/or separations. While previous reports have discussed dissolution of zerovalent metals, the resulting oxidation states of coordination complexes have proved difficult to interpret through X-ray crystallographic analysis alone. This report describes the X-ray crystallographic analysis combined with computational modelling of the ATF ligand and metal complexes to deconvolute the metal and ligand oxidation state of metal-ATF complexes. Metal(ATF)2 complexes that originated from zerovalent metals were found to exist as dicationic metal centers containing two singly reduced ATF ligands. When employing Cu(I) salts instead of Cu(0) to generate copper-ATF complexes, the resulting complexes remained Cu(I) and the ATF ligand remained "innocent", existing in its neutral state. Although the use of CuX (where X = Br or I) or [Cu(NCMe)4]Y (where Y = BF4 or PF6) generated species of the type: [(ATF)Cu(µ-X)]2 and [Cu(ATF)2]Y, respectively, the ATF ligand remained in its neutral state for each species type.

Electronic and Steric Influences of Pendant Amine Groups on the Protonation of Molybdenum Bis(dinitrogen) Complexes.

The synthesis of a series of P(Et)P(NRR(')) (P(Et)P(NRR(')) = Et2PCH2CH2P(CH2NRR')2, R = H, R' = Ph or 2,4-difluorophenyl; R = R' = Ph or (i)Pr) diphosphine ligands containing mono- and disubstituted pendant amine groups and the preparation of their corresponding molybdenum bis(dinitrogen) complexes trans-Mo(N2)2(PMePh2)2(P(Et)P(NRR('))) is described. In situ IR and multinuclear NMR spectroscopic studies monitoring the stepwise addition of triflic acid (HOTf) to trans-Mo(N2)2(PMePh2)2(P(Et)P(NRR('))) complexes in tetrahydrofuran at -40 °C show that the electronic and steric properties of the R and R' groups of the pendant amines influence whether the complexes are protonated at Mo, a pendant amine, a coordinated N2 ligand, or a combination of these sites. For example, complexes containing monoaryl-substituted pendant amines are protonated at Mo and the pendant amine site to generate mono- and dicationic Mo-H species. Protonation of the complex containing less basic diphenyl-substituted pendant amines exclusively generates a monocationic hydrazido (Mo(NNH2)) product, indicating preferential protonation of an N2 ligand. Addition of HOTf to the complex featuring more basic diisopropyl amines primarily produces a monocationic product protonated at a pendant amine site, as well as a trace amount of dicationic Mo(NNH2) product that is additionally protonated at a pendant amine site. In addition, trans-Mo(N2)2(PMePh2)2(depe) (depe = Et2PCH2CH2PEt2) was synthesized to serve as a counterpart lacking pendant amines. Treatment of this complex with HOTf generated a monocationic Mo(NNH2) product. Protonolysis experiments conducted on several complexes in this study afforded trace amounts of NH4(+). Computational analysis of trans-Mo(N2)2(PMePh2)2(P(Et)P(NRR('))) complexes provides further insight into the proton affinity values of the metal center, N2 ligand, and pendant amine sites to rationalize differences in their reactivity profiles.

Discovery of low energy pathways to metal-mediated B[double bond, length as m-dash]N bond reduction guided by computation and experiment.

This manuscript describes a combination of DFT calculations and experiments to assess the reduction of borazines (B-N heterocycles) by η6-coordination to Cr(CO)3 or [Mn(CO)3]+ fragments. The energy requirements for borazine reduction are established as well as the extent to which coordination of borazine to a transition metal influences hydride affinity, basicity, and subsequent reduction steps at the coordinated borazine molecule. Borazine binding to M(CO)3 fragments decreases the thermodynamic hydricity by >30 kcal mol-1, allowing it to easily accept a hydride. These hydricity criteria were used to guide the selection of appropriate reagents for borazine dearomatization. Reduction was achieved with an H2-derived hydride source, and importantly, a pathway which proceeds through a single electron reduction and H-atom transfer reaction, mediated by anthraquinone was uncovered. The latter transformation was also carried out electrochemically, at relatively positive potentials by comparison to all prior reports, thus establishing an important proof of concept for any future electrochemical B[double bond, length as m-dash]N bond reduction.

Protonation of ferrous dinitrogen complexes containing a diphosphine ligand with a pendent amine.

The addition of acids to ferrous dinitrogen complexes [FeX(N2)(P(Et)N(Me)P(Et))(dmpm)](+) (X = H, Cl, or Br; P(Et)N(Me)P(Et) = Et2PCH2N(Me)CH2PEt2; and dmpm = Me2PCH2PMe2) gives protonation at the pendent amine of the diphosphine ligand rather than at the dinitrogen ligand. This protonation increased the νN2 band of the complex by 25 cm(-1) and shifted the Fe(II/I) couple by 0.33 V to a more positive potential. A similar IR shift and a slightly smaller shift of the Fe(II/I) couple (0.23 V) was observed for the related carbonyl complex [FeH(CO)(P(Et)N(Me)P(Et))(dmpm)](+). [FeH(P(Et)N(Me)P(Et))(dmpm)](+) was found to bind N2 about three times more strongly than NH3. Computational analysis showed that coordination of N2 to Fe(II) centers increases the basicity of N2 (vs free N2) by 13 and 20 pKa units for the trans halides and hydrides, respectively. Although the iron center increases the basicity of the bound N2 ligand, the coordinated N2 is not sufficiently basic to be protonated. In the case of ferrous dinitrogen complexes containing a pendent methylamine, the amine site was determined to be the most basic site by 30 pKa units compared to the N2 ligand. The chemical reduction of these ferrous dinitrogen complexes was performed in an attempt to increase the basicity of the N2 ligand enough to promote proton transfer from the pendent amine to the N2 ligand. Instead of isolating a reduced Fe(0)-N2 complex, the reduction resulted in isolation and characterization of HFe(Et2PC(H)N(Me)CH2PEt2)(P(Et)N(Me)P(Et)), the product of oxidative addition of the methylene C-H bond of the P(Et)N(Me)P(Et) ligand to Fe.

Metal-free aromatic hydrogenation: aniline to cyclohexyl-amine derivatives.

Hydrogenation of the N-bound phenyl rings of amines, imines, and aziridine is achieved in the presence of H(2) and B(C(6)F(5))(3), affording the corresponding N-cyclohexylammonium hydridoborate salts.