Catalytic Ammonia Oxidation to Dinitrogen by a Nickel Complex.

We report a nickel complex for catalytic oxidation of ammonia to dinitrogen under ambient conditions. Using the aryloxyl radical 2,4,6-tri-tert-butylphenoxyl (t Bu3 ArO⋅) as a H atom acceptor to cleave the N-H bond of a coordinated NH3 ligand up to 56 equiv of N2 per Ni center can be generated. Employing the N-oxyl radical 2,2,6,6-(tetramethylpiperidin-1-yl)oxyl (TEMPO⋅) as the H-atom acceptor, up to 15 equiv of N2 per Ni center are formed. A bridging Ni-hydrazine product identified by isotopic nitrogen (15 N) studies and supported by computational models indicates the N-N bond forming step occurs by bimetallic homocoupling of two paramagnetic [Ni]-NH2 fragments. Ni-mediated hydrazine disproportionation to N2 and NH3 completes the catalytic cycle.

H2 Binding, Splitting, and Net Hydrogen Atom Transfer at a Paramagnetic Iron Complex.

While diamagnetic transition metal complexes that bind and split H2 have been extensively studied, paramagnetic complexes that exhibit this behavior remain rare. The square planar S = 1/2 FeI(P4N2)+ cation (FeI+) reversibly binds H2/D2 in solution, exhibiting an inverse equilibrium isotope effect of KH2/ KD2 = 0.58(4) at -5.0 °C. In the presence of excess H2, the dihydrogen complex FeI(H2)+ cleaves H2 at 25 °C in a net hydrogen atom transfer reaction, producing the dihydrogen-hydride trans-FeII(H)(H2)+. The proposed mechanism of H2 splitting involves both intra- and intermolecular steps, resulting in a mixed first- and second-order rate law with respect to initial [FeI+]. The key intermediate is a paramagnetic dihydride complex, trans-FeIII(H)2+, whose weak FeIII-H bond dissociation free energy (calculated BDFE = 44 kcal/mol) leads to bimetallic H-H homolysis, generating trans-FeII(H)(H2)+. Reaction kinetics, thermodynamics, electrochemistry, EPR spectroscopy, and DFT calculations support the proposed mechanism.

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.

Catalytic Silylation of N2 and Synthesis of NH3 and N2H4 by Net Hydrogen Atom Transfer Reactions Using a Chromium P4 Macrocycle.

We report the first discrete molecular Cr-based catalysts for the reduction of N2. This study is focused on the reactivity of the Cr-N2 complex, trans-[Cr(N2)2(PPh4NBn4)] (P4Cr(N2)2), bearing a 16-membered tetraphosphine macrocycle. The architecture of the [16]-PPh4NBn4 ligand is critical to preserve the structural integrity of the catalyst. P4Cr(N2)2 was found to mediate the reduction of N2 at room temperature and 1 atm pressure by three complementary reaction pathways: (1) Cr-catalyzed reduction of N2 to N(SiMe3)3 by Na and Me3SiCl, affording up to 34 equiv N(SiMe3)3; (2) stoichiometric reduction of N2 by protons and electrons (for example, the reaction of cobaltocene and collidinium triflate at room temperature afforded 1.9 equiv of NH3, or at -78 °C afforded a mixture of NH3 and N2H4); and (3) the first example of NH3 formation from the reaction of a terminally bound N2 ligand with a traditional H atom source, TEMPOH (2,2,6,6-tetramethylpiperidine-1-ol). We found that trans-[Cr(15N2)2(PPh4NBn4)] reacts with excess TEMPOH to afford 1.4 equiv of 15NH3. Isotopic labeling studies using TEMPOD afforded ND3 as the product of N2 reduction, confirming that the H atoms are provided by TEMPOH.

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]+.

Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at Square Planar Fe.

The geometric constraints imposed by a tetradentate P4N2 ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe0(N2)(P4N2) complex catalyzes the conversion of N2 to N(SiR3)3 (R = Me, Et) at room temperature, representing the highest turnover number of any Fe-based N2 silylation catalyst to date (up to 65 equiv N(SiMe3)3 per Fe center). Elevated N2 pressures (>1 atm) have a dramatic effect on catalysis, increasing N2 solubility and the thermodynamic N2 binding affinity at Fe0(N2)(P4N2). A combination of high-pressure electrochemistry and variable-temperature UV-vis spectroscopy were used to obtain thermodynamic measurements of N2 binding. In addition, X-ray crystallography, 57Fe Mössbauer spectroscopy, and EPR spectroscopy were used to fully characterize these new compounds. Analysis of Fe0, FeI, and FeII complexes reveals that the free energy of N2 binding across three oxidation states spans more than 37 kcal mol-1.

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 studies of a mono-dinitrogen complex of chromium supported by a 12-membered phosphorus macrocycle containing pendant amines.

The reduction of fac-[CrCl3(P(Ph)3N(Bn)3)], (1(Cl3)), (P(Ph)3N(Bn)3 = 1,5,9-tribenzyl-3,7,11-triphenyl-1,5,9-triaza-3,7,11-triphosphacyclododecane) with Mg in the presence of dmpe (dmpe = 1,2-bis(dimethylphosphino)ethane) affords the first example of a monodinitrogen Cr(0) complex, Cr(N2)(dmpe)(P(Ph)3N(Bn)3), (2(N2)), containing a pentaphosphine coordination environment. 2(N2) is supported by a unique facially coordinating 12-membered phosphorus macrocycle containing pendant amine groups in the second coordination sphere. Treatment of 2(N2) at -78 °C with 1 equiv of [H(OEt2)2][B(C6F5)4] results in protonation of the metal center, generating the seven-coordinate Cr(II)-N2 hydride complex, [Cr(H)(N2)(dmpe)(P(Ph)3N(Bn)3)][B(C6F5)4], [2(H)(N2)](+). Treatment of 2((15)N2) with excess triflic acid at -50 °C afforded a trace amount of (15)NH4(+) from the reduction of the coordinated (15)N2 ligand (electrons originate from Cr). Electronic structure calculations were employed to evaluate the pKa values of three protonated sites of 2(N2) (metal center, pendant amine, and N2 ligand) and were used to predict the thermodynamically preferred Cr-NxHy intermediates in the N2 reduction pathway for 2(N2) and the recently published complex trans-[Cr(N2)2(P(Ph)4N(Bn)4)] upon the addition of protons and electrons.

Dinitrogen activation at chromium by photochemically induced CrII-C bond homolysis.

The synthesis of the organochromium(II) complexes [POCOPtBu]Cr(R) (R = p-Tol, Bn) is reported. Exposure of [POCOPtBu]Cr(Bn) to visible light promoted homolytic Cr-CBn bond cleavage and formed {[POCOPtBu]Cr}2(η1:η1µ-N2) via a putative [POCOPtBu]Cr(I) species.

Catalytic dinitrogen reduction to hydrazine and ammonia using Cr(N2)2(diphosphine)2 complexes.

The synthesis, characterization of trans-[Cr(N2)2(depe)2] (1) is described. 1 and trans-[Cr(N2)2(dmpe)2] (2) catalyze the reduction of N2 to N2H4 and NH3 in THF using SmI2 and H2O or ethylene glycol as proton sources. 2 produces the highest total fixed N for a molecular Cr catalyst to date.

Halide-free synthesis of metastable graphitic BC3.

Layered BC3, a metastable phase within the binary boron-carbon system that is composed of graphite-like sheets with hexagonally symmetric C6B6 units, has never been successfully crystallized. Instead, poorly-crystalline BC3-like materials with significant stacking disorder have been isolated, based on the co-pyrolysis of a boron trihalide precursor with benzene at around 800 °C. The halide leaving group (-X) is a significant driving force of these reactions, but the subsequent evolution of gaseous HX species at such high temperatures hampers their scaling up and also prohibits their further use in the presence of hard-casting templates such as ordered silicates. Herein, we report a novel halide-free synthesis route to turbostratic BC3 with long-range in-plane ordering, as evidenced by multi-wavelength Raman spectroscopy. Judicious pairing of the two molecular precursors is crucial to achieving B-C bond formation and preventing phase-segregation into the thermodynamically favored products. A simple computational method used herein to evaluate the compatibility of bottom-up molecular precursors can be generalized to guide the future synthesis of other metastable materials beyond the boron-carbon system.

A cobalt-based catalyst for the hydrogenation of CO2 under ambient conditions.

Because of the continually rising levels of CO2 in the atmosphere, research for the conversion of CO2 into fuels using carbon-neutral energy is an important and current topic in catalysis. Recent research on molecular catalysts has led to improved rates for conversion of CO2 to formate, but the catalysts are based on precious metals such as iridium, ruthenium and rhodium and require high temperatures and high pressures. Using established thermodynamic properties of hydricity (ΔGH(-)) and acidity (pKa), we designed a cobalt-based catalyst system for the production of formate from CO2 and H2. The complex Co(dmpe)2H (dmpe is 1,2-bis(dimethylphosphino)ethane) catalyzes the hydrogenation of CO2, with a turnover frequency of 3400 h(-1) at room temperature and 1 atm of 1:1 CO2:H2 (74,000 h(-1) at 20 atm) in tetrahydrofuran. These results highlight the value of fundamental thermodynamic properties in the rational design of catalysts.

Dinitrogen reduction by a chromium(0) complex supported by a 16-membered phosphorus macrocycle.

We report a rare example of a Cr-N2 complex supported by a 16-membered phosphorus macrocycle containing pendant amine bases. Reactivity with acid afforded hydrazinium and ammonium, representing the first example of N2 reduction by a Cr-N2 complex. Computational analysis examined the thermodynamically favored protonation steps of N2 reduction with Cr leading to the formation of hydrazine.

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.

Synthesis, characterization, and liquid injection field desorption ionization mass spectrometry analysis of pincer ligated group 6 (Cr, Mo, W) carbonyl complexes.

We report the synthesis of molybdenum and tungsten bromo dicarbonyl complexes (POCOPtBu)MIIBr(CO)2 (M = Mo or W; POCOPtBu = κ3-C6H3-1,3-[OP(tBu)2]2) supported by an anionic PCP pincer ligand, and the chromium complex (PNPtBu)Cr0(CO)3 (PNPtBu = 2,6-bis(di-tert-butyl-phosphinomethyl)pyridine) bearing a neutral PNP pincer scaffold. The three group six complexes described in this study have been characterized by Liquid Injection Field Desorption Ionization Mass Spectrometry (LIFDI-MS), NMR, and IR spectroscopy. Single crystal X-ray diffraction studies show the MoII and WII complexes adopt a six-coordinate distorted trigonal prismatic geometry, whereas the Cr0 complex exhibits a distorted octahedral geometry.

Semisynthetic maturation of [FeFe]-hydrogenase using [Fe2(µ-SH)2(CN)2(CO)4]2-: key roles for HydF and GTP.

Here we describe maturation of the [FeFe]-hydrogenase from its [4Fe-4S]-bound precursor state by using the synthetic complex [Fe2(µ-SH)2(CN)2(CO)4]2- together with HydF and components of the glycine cleavage system, but in the absence of the maturases HydE and HydG. This semisynthetic and fully-defined maturation provides new insights into the nature of H-cluster biosynthesis.

Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds.

Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H(2) gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)(2) (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX(3) compounds having a hydride affinity (HA) greater than or equal to the HA of BEt(3). This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)(2) and [HNi(dmpe)(2)](+), to form B-H bonds. The hydride donor abilities (ΔG(H(-))°) of HCo(dmpe)(2) and [HNi(dmpe)(2)](+) were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX(3) compounds. The collective data guided our selection of BX(3) compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)(2) was observed to transfer H(-) to BX(3) compounds with X = H, OC(6)F(5), and SPh. The reaction with B(SPh)(3) is accompanied by the formation of dmpe-(BH(3))(2) and dmpe-(BH(2)(SPh))(2) products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)(2) and B(SPh)(3) in the presence of triethylamine result in the formation of Et(3)N-BH(2)SPh and Et(3)N-BH(3) with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)(2)](+) with B(SPh)(3) under analogous conditions give Et(3)N-BH(2)SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)(2)(SPh)](+). The synthesis and characterization of HCo(dedpe)(2) (dedpe = Et(2)PCH(2)CH(2)PPh(2)) from H(2) and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)(2)Co(dedpe)(2)][BF(4)].

Thermodynamic studies and hydride transfer reactions from a rhodium complex to BX3 compounds.

This study examines the use of transition-metal hydride complexes that can be generated by the heterolytic cleavage of H(2) gas to form B-H bonds. Specifically, these studies are focused on providing a reliable and quantitative method for determining when hydride transfer from transition-metal hydrides to three-coordinate BX(3) (X = OR, SPh, F, H; R = Ph, p-C(6)H(4)OMe, C(6)F(5), (t)Bu, Si(Me)(3)) compounds will be favorable. This involves both experimental and theoretical determinations of hydride transfer abilities. Thermodynamic hydride donor abilities (DeltaG(o)(H(-))) were determined for HRh(dmpe)(2) and HRh(depe)(2), where dmpe = 1,2-bis(dimethylphosphinoethane) and depe = 1,2-bis(diethylphosphinoethane), on a previously established scale in acetonitrile. This hydride donor ability was used to determine the hydride donor ability of [HBEt(3)](-) on this scale. Isodesmic reactions between [HBEt(3)](-) and selected BX(3) compounds to form BEt(3) and [HBX(3)](-) were examined computationally to determine their relative hydride affinities. The use of these scales of hydride donor abilities and hydride affinities for transition-metal hydrides and BX(3) compounds is illustrated with a few selected reactions relevant to the regeneration of ammonia borane. Our findings indicate that it is possible to form B-H bonds from B-X bonds, and the extent to which BX(3) compounds are reduced by transition-metal hydride complexes forming species containing multiple B-H bonds depends on the heterolytic B-X bond energy. An example is the reduction of B(SPh)(3) using HRh(dmpe)(2) in the presence of triethylamine to form Et(3)N-BH(3) in high yields.

A high-spin organometallic Fe-S compound: structural and Mössbauer spectroscopic studies of [phenyltris((tert-butylthio)methyl)borate]Fe(Me).

The synthesis and structure of the pseudotetrahedral, sulfur-rich, high-spin organoiron(II) [phenyltris((tert-butylthio)methyl)borate]Fe(Me), [PhTt(tBu)]Fe(Me), 1, are reported. Low-temperature Mössbauer spectroscopic studies reveal an isomer shift of delta = 0.60(3) mm/s and DeltaE(Q) = 0.00(1) mm/s and an S = 2 ground multiplet with a negative zero-field splitting, D = -33(3) cm(-1), E/D approximately = 0.01. The small separation of the ground doublet, Delta approximately = 0.01 cm(-1), allows for observation of X-band EPR signals at g(eff) approximately = 10 (g(z) = 2.6, g(x,y) = 2.00). The relatively large negative zero-field splitting and a highly anisotropic magnetic hyperfine tensor, containing a large orbital z component, {-10(4), -10(4), +33.8(2) MHz}, are concordant with the presence of unquenched orbital angular momentum. Density functional theory (DFT) calculations predict that the lowest-lying orbitals have predominantly d(xy)- and d(x(2)-y(2))-like character, separated by an energy gap small enough to allow mixing through spin-orbit coupling, to generate a negative zero-field splitting, consistent with the experimental observations. The experimental and DFT-calculated isomer shifts are in good agreement (delta(calcd) = 0.5 mm/s). The unusual (for a high-spin ferrous site) null electric field gradients can be qualitatively explained in the frame of the spin-orbit coupling mixing. The very small Fermi contact component of the magnetic hyperfine tensor (A(FC)(exp) = -9 MHz) is not well described by the DFT approach (A(FC)(calcd) = +2 MHz). To our knowledge, this is the first study of a sulfur-coordinated high-spin organoiron(II) complex.

A Series of Cyanide-Bridged Binuclear Complexes.

A series of cyanide-bridged binuclear complexes, ('S(3)')Ni-CN-M[Tp(tBu)] ('S(3)' = bis(2-mercaptophenyl)sulfide, Tp(tBu) = hydrotris(3-tert-butylpyrazolyl)borate, M = Fe (2-Fe), Co (2-Co), Ni (2-Ni), Zn (2-Zn)) was prepared by the coupling of K[('S(3)')Ni(CN)] with [Tp(tBu)]MX. The isostructural series of complexes was structurally and spectroscopically characterized. A similar coupling strategy was used to synthesize the anionic copper(I) analogue, Et4N{('S3')Ni-CN-Cu[Tp(tBu)]}, 2-Cu.An alternative synthesis was devised for the preparation of the linkages isomers of 2-Zn, i.e. of cyanide-bridged linkage isomers. X-ray diffraction, (13)C NMR and IR spectral studies established that isomerization to the more stable Ni-CN-Zn isomer occurs. DFT computational results buttressed the experimental observations indicating that the cyanide-bridged isomer is ca. 5 kcal/mol more stable than its linkage isomer.