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.

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.

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.

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.

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.

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.

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.

Synthesis and reactivity of o-benzylphosphino- and o-α-methylbenzyl(N,N-dimethyl)amine-boranes.

The series of o-benzylphosphino-boranes, o-(R(2)B)C(6)H(4)CH(2)PtBu(2) (R = Cl 3, Ph 4, Cy 6, C(6)F(5) 7, Mes 8) and o-(BBN)C(6)H(4)CH(2)PtBu(2) (5), were synthesized from reactions of the respective chloroboranes with the lithiated benzyl-phosphine. In an analogous fashion, the α-methylbenzyl(N,N-dimethyl)amine-boranes o-(R(2)B)C(6)H(4)CH(Me)NMe(2) (R = Cl 10, Ph 11, Cy 12, C(6)F(5) 13, Mes 14) were prepared. While these species were inactive in the catalytic hydrogenation of tBuN═CHPh, compounds 7, 8, and 14 did react with H(2) at elevated temperatures (100 °C), resulting in the elimination of HC(6)F(5) and mesitylene, respectively. In the latter case, the species o-((Mes)HB)C(6)H(4)CH(Me)NMe(2) 15 was isolated. 14 was also shown to react with H(2)O to give the species o-((Mes)(HO)B)C(6)H(4)CH(Me)NMe(2) 16 with the loss of mesitylene. The structure of these compounds and the nature of these reactions were also probed spectroscopically, crystallographically, and computationally. The energies for the products of hydrogenation, the phosphonium and ammonium hydridoborates, were computed. In all cases, these products were endothermic with respect to the precursor phosphine-boranes and amine-boranes and H(2). The barriers to H(2) activation were found to be in the range of 24-38 kcal/mol. These theoretical studies also demonstrate that the steric bulk around the boron center dramatically affects the activation barrier for H(2) activation, while the Lewis acidity of the borane has the largest effect on the stabilization of the resulting onium-borohydride. In the case of the elimination reactions, the driving forces appear to be the loss of arene byproduct and formation of a strong donor-acceptor bond.

Coordination chemistry of the soft chiral Lewis acid [Cp*Ir(TsDPEN)]+.

The paper surveys the binding of anions to the unsaturated 16e Lewis acid [Cp*Ir(TsDPEN)](+) ([1H](+)), where TsDPEN is racemic H(2)NCHPhCHPhNTs(-). The derivatives Cp*IrX(TsDPEN) were characterized crystallographically for X(-) = CN(-), Me(C═NH)S(-), NO(2)(-), 2-pyridonate, and 0.5 MoS(4)(2-). [(1H)(2)(µ-CN)](+) forms from [1H](+) and 1H(CN). Aside from 2-pyridone, amides generally add reversibly and bind to Ir through N. Thioacetamide binds irreversibly through sulfur. Compounds of the type Cp*IrX(TsDPEN) generally form diastereoselectively, although diastereomeric products were observed for the strong ligands (X = CN(-), H(-) (introduced via BH(4)(-)), or Me(C═NH)S(-)). Related experiments on the reaction (p-cymene)Ru(TsDPEN-H) + BH(4)(-) gave two diastereomers of (p-cymene)RuH(TsDPEN), the known hydrogenation catalyst and a second isomer that hydrogenated acetophenone more slowly. These experiment provide new insights into the enantioselectivity of these catalysts. Diastereomerization in all cases was first order in metal with modest solvent effects. The diphenyl groups are generally diequatorial for the stable diastereomers. For the 2-pyridonate adduct, axial phenyl groups are stabilized in the solid state by puckering of the IrN(2)C(2) ring induced by intramolecular hydrogen-bonding. Crystallographic analysis of [Cp*Ir(TsDPEN)](2)(MoS(4)) revealed a unique example of a κ(1),κ(1)-tetrathiometallate ligand. Cp*Ir(SC(NH)Me)TsDPEN) is the first example of a κ(1)-S-thioamidato complex.

Metal-free catalytic hydrogenation of polar substrates by frustrated Lewis pairs.

In 2006, our group reported the first metal-free systems that reversibly activate hydrogen. This finding was extended to the discovery of "frustrated Lewis pair" (FLP) catalysts for hydrogenation. It is this catalysis that is the focal point of this article. The development and applications of such FLP hydrogenation catalysts are reviewed, and some previously unpublished data are reported. The scope of the substrates is expanded. Optimal conditions and functional group tolerance are considered and applied to targets of potential commercial significance. Recent developments in asymmetric FLP hydrogenations are also reviewed. The future of FLP hydrogenation catalysts is considered.

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.

Proton-assisted activation of dihydrogen: mechanistic aspects of proton-catalyzed addition of H2 to Ru and Ir amido complexes.

This study examines the acid-catalyzed hydrogenation of ketones by amido-amine chelates of Ru and Ir, focusing on the hydrogen activation step. Addition of H(2) to the catalyst Cp*Ir(TsDPEN-H) (1, TsDPEN = racemic H(2)NCHPhCHPhNTs(-)) is more favorable than for corresponding (cymene)Ru derivatives. Depending on the acid, the rate of the proton-catalyzed addition of H(2) to 1 varies over 3 orders of magnitude even for strong acids. Acids protonate the NH center in the five-coordinate diamides to give the amido-amine, e.g., [Cp*Ir(TsDPEN)](+) ([1H](+)). The rate of proton-catalyzed hydrogenation of 1 was found to be first order in both H(2) and in [1H](+) for X(-) = BF(4)(-), OTf(-), ClO(4)(-), NO(3)(-). For X(-) = ClO(4)(-) and BAr(F)(4)(-) (BAr(F)(4)(-) = B(C(6)H(3)-3,5-(CF(3))(2))(4)(-)), the rate showed an additional dependence on [1]. The hydrogenation of 1 is proposed to occur via the dihydrogen complex ([1H(H(2))](+)) followed by proton transfer to 1, either directly (third-order pathway) or via anion-assisted proton transfer (second-order pathway). The pK(a) (H-H bond) of [1H(H(2))](+) is predicted to be 13.88 +/- 0.37 (MeCN solution) whereas the pK(a) (N-H bond) of [1H](+) is about 21.6. The rate of hydrogenation of 1 was fastest for acids about 3 orders of magnitude (pK(a) approximately 10) more acidic than [1H(H(2))](+), but slower for stronger acids. Although the affinity of H(2) for [Cp*Ir(TsDPEN)](+) is orders of magnitude lower than for 1 (298 K), the cationic complex adds H(2) far faster. Similar trends are seen for (cymene)Ru(TsDPEN-H) (2) and its derivatives. The affinity of H(2) for 2 was found to be 3x less than for 1.

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.

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.

Redox-switched oxidation of dihydrogen using a non-innocent ligand.

Organometallic complexes containing non-innocent ligands of the type Cp*Ir(tBAFPh)(1), where H2tBAFPh is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, were found to activate H2 in a redox-switchable manner. The 16e- complex 1 was inert with respect to H2, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag+ resulted in ligand-centered oxidation affording salts of [1]+, which were characterized by crystallographically, EPR, and elemental analyses. [1]+ was reduced to 1 in the presence of H2 and the sterically hindered base, 2,6-(tBu)2C5H3N, via a pathway that is first-order in both metal and dihydrogen. Compound [1]+ forms adducts with MeCN, which inhibits catalysis. The catalytic oxidation of H2 was established by electrochemical methods to be associated with the monocation.

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.