Charles Edwin Webster

Development of Ultrafast Photochromic Organometallics and Photoinduced Linkage Isomerization of Arene Chromium Carbonyl Derivatives

We review recent studies of processes relevant to photoinduced linkage isomerization of organometallic systems with the goal of preparing organometallics with an efficient and ultrafast photochromic response. The organometallic system thus corresponds to two linkage isomers with different electronic environments that are responsible for different optical properties. Much of this work has focused on examining processes following irradiation of cyclopentadienyl manganese tricarbonyl derivatives (compounds 3-21) including solvent coordination, thermal relaxation, solvent displacement by tethered functional groups (chelation), dissociation of tethered functional groups, and linkage isomerization. A new platform is investigated for obtaining a photochromic response in new experiments with arene chromium dicarbonyl complexes. A photochromic response is observed for arene chromium dicarbonyl complexes with tethered pyridine and olefin functional groups based on light-driven linkage isomerization on the nanosecond time scale. Irradiation at 532 nm of 23 ([Cr{eta(6)-C(6)H(5)CH(2-Py-kappaN)CH(2)CH=CH(2)}(CO)(2)]) (Py = pyridine) results in the isomerization to 22 ([Cr{eta(6)-C(6)H(5)CH(2-Py)CH(2)-eta(2)-CH=CH(2)}(CO)(2)]), and 355 nm irradiation isomerizes 22 to 23. The ultrafast linkage isomerization has been investigated at room temperature in n-heptane solution on the picosecond to microsecond time scale with UV- or visible-pump and IR-probe transient absorption spectroscopy by comparing the dynamics with model compounds containing only a tethered pyridine. Irradiation of 24 ([Cr{eta(6)-C(6)H(5)(CH(2))(3)(2-Py)}(CO)(3)]) and 25 ([Cr{eta(6)-C(6)H(5)(CH(2))(2)(2-Py)}(CO)(3)]) at 289 nm induces CO loss to immediately yield a Cr-heptane solvent coordinated intermediate of the unsaturated Cr fragment, which then converts to the kappaN(1)-pyridine chelate within 200 and 100 ns, respectively. Irradiation of 26 ([Cr{eta(6)-C(6)H(5)CH(2)(2-Py)}(CO)(3)]) also induces CO loss to immediately yield three species: the Cr-heptane solvent coordinated intermediate, a kappaN(1)-Py nitrogen chelate, and an agostic eta(2)-chelate in which the pyridine is coordinated to the metal center via a C-H agostic bond as opposed to the nitrogen lone pair. Both the transient Cr-heptane coordinated intermediate and the agostic pyridine chelate convert to the stable kappaN(1)-pyridine chelate within 50 ns. Similar reaction dynamics and transient species are observed for the chelate 33 ([Cr{eta(6)-C(6)H(5)CH(2)(2-Py)-kappaN}(CO)(2)]) where a Cr-Py bond, not a Cr-CO bond, initially cleaves.

Near attack conformers dominate β-phosphoglucomutase complexes where geometry and charge distribution reflect those of substrate

Experimental observations of fluoromagnesate and fluoroaluminate complexes of β-phosphoglucomutase (β-PGM) have demonstrated the importance of charge balance in transition-state stabilization for phosphoryl transfer enzymes. Here, direct observations of ground-state analog complexes of β-PGM involving trifluoroberyllate establish that when the geometry and charge distribution closely match those of the substrate, the distribution of conformers in solution and in the crystal predominantly places the reacting centers in van der Waals proximity. Importantly, two variants are found, both of which satisfy the criteria for near attack conformers. In one variant, the aspartate general base for the reaction is remote from the nucleophile. The nucleophile remains protonated and forms a nonproductive hydrogen bond to the phosphate surrogate. In the other variant, the general base forms a hydrogen bond to the nucleophile that is now correctly orientated for the chemical transfer step. By contrast, in the absence of substrate, the solvent surrounding the phosphate surrogate is arranged to disfavor nucleophilic attack by water. Taken together, the trifluoroberyllate complexes of β-PGM provide a picture of how the enzyme is able to organize itself for the chemical step in catalysis through the population of intermediates that respond to increasing proximity of the nucleophile. These experimental observations show how the enzyme is capable of stabilizing the reaction pathway toward the transition state and also of minimizing unproductive catalysis of aspartyl phosphate hydrolysis.

Time-resolved IR studies on the mechanism for the functionalization of primary C-H bonds by photoactivated Cp*W(CO)3(Bpin)

Recently, transition-metal-boryl compounds have been reported that selectively functionalize primary C-H bonds in alkanes in high yield. We have investigated this process with one of the well-defined systems that reacts under photochemical conditions using both density functional theory calculations and pico- through microsecond time-resolved IR spectroscopy. UV irradiation of Cp*W(CO)(3)(Bpin) (Cp* = C(5)(CH(3))(5); pin = 1,2-O(2)C(2)-(CH(3))(4)) in neat pentane solution primarily results in dissociation of a single CO ligand and solvation of the metal by a pentane molecule from the bath within 2 ps. The spectroscopic data imply that the resulting complex, cis-Cp*W(CO)(2)(Bpin)(pentane), undergoes C-H bond activation by a sigma-bond metathesis mechanism--in 16 micros, a terminal hydrogen on pentane appears to migrate to the Bpin ligand to form a sigma-borane complex, Cp*W(CO)(2)(H-Bpin)(C(5)H(11)). Our data imply that the borane ligand rotates until the boron is directly adjacent to the C(5)H(11) ligand. In this configuration, the B-H sigma-bond is broken in favor of a B-C sigma-bond, forming Cp*W(CO)(2)(H)(C(5)H(11)-Bpin), a tungsten-hydride complex containing a weakly bound alkylboronate ester. The ester is then eliminated to form Cp*W(CO)(2)(H) in approximately 170 micros. We also identify two side reactions that limit the total yield of bond activation products and explain the 72% yield previously reported for this complex.

Iridium and Ruthenium Complexes of N-Heterocyclic Carbene- and Pyridinol-Derived Chelates as Catalysts for Aqueous Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation: The Role of the Alkali Metal

Hydrogenation reactions can be used to store energy in chemical bonds, and if these reactions are reversible, that energy can be released on demand. Some of the most effective transition metal catalysts for CO2 hydrogenation have featured pyridin-2-ol-based ligands (e.g., 6,6′-dihydroxybipyridine (6,6′-dhbp)) for both their proton-responsive features and for metal–ligand bifunctional catalysis. We aimed to compare bidentate pyridin-2-ol based ligands with a new scaffold featuring an N-heterocyclic carbene (NHC) bound to pyridin-2-ol. Toward this aim, we have synthesized a series of [Cp*Ir(NHC-pyOR)Cl]OTf complexes where R = tBu (1), H (2), or Me (3). For comparison, we tested analogous bipy-derived iridium complexes as catalysts, specifically [Cp*Ir(6,6′-dxbp)Cl]OTf, where x = hydroxy (4Ir) or methoxy (5Ir); 4Ir was reported previously, but 5Ir is new. The analogous ruthenium complexes were also tested using [(η6-cymene)Ru(6,6′-dxbp)Cl]OTf, where x = hydroxy (4Ru) or methoxy (5Ru); 4Ru and 5Ru were both reported previously. All new complexes were fully characterized by spectroscopic and analytical methods and by single-crystal X-ray diffraction for 1, 2, 3, 5Ir, and for two [Ag(NHC-pyOR)2]OTf complexes 6 (R = tBu) and 7 (R = Me). The aqueous catalytic studies of both CO2 hydrogenation and formic acid dehydrogenation were performed with catalysts 1–5. In general, NHC-pyOR complexes 1–3 were modest precatalysts for both reactions. NHC complexes 1–3 all underwent transformations under basic CO2 hydrogenation conditions, and for 3, we trapped a product of its transformation, 3SP, which we characterized crystallographically. For CO2 hydrogenation with base and dxbp-based catalysts, we observed that x = hydroxy (4Ir) is 5–8 times more active than x = methoxy (5Ir). Notably, ruthenium complex 4Ru showed 95% of the activity of 4Ir. For formic acid dehydrogenation, the trends were quite different with catalytic activity showing 4Ir ≫ 4Ru and 4Ir ≈ 5Ir. Secondary coordination sphere effects are important under basic hydrogenation conditions where the OH groups of 6,6′-dhbp are deprotonated and alkali metals can bind and help to activate CO2. Computational DFT studies have confirmed these trends and have been used to study the mechanisms of both CO2 hydrogenation and formic acid dehydrogenation.

Time-resolved vibrational spectroscopy of [FeFe]-hydrogenase model compounds.

Model compounds have been found to structurally mimic the catalytic hydrogen-producing active site of Fe-Fe hydrogenases and are being explored as functional models. The time-dependent behavior of Fe(2)(μ-S(2)C(3)H(6))(CO)(6) and Fe(2)(μ-S(2)C(2)H(4))(CO)(6) is reviewed and new ultrafast UV- and visible-excitation/IR-probe measurements of the carbonyl stretching region are presented. Ground-state and excited-state electronic and vibrational properties of Fe(2)(μ-S(2)C(3)H(6))(CO)(6) were studied with density functional theory (DFT) calculations. For Fe(2)(μ-S(2)C(3)H(6))(CO)(6) excited with 266 nm, long-lived signals (τ = 3.7 ± 0.26 μs) are assigned to loss of a CO ligand. For 355 and 532 nm excitation, short-lived (τ = 150 ± 17 ps) bands are observed in addition to CO-loss product. Short-lived transient absorption intensities are smaller for 355 nm and much larger for 532 nm excitation and are assigned to a short-lived photoproduct resulting from excited electronic state structural reorganization of the Fe-Fe bond. Because these molecules are tethered by bridging disulfur ligands, this extended di-iron bond relaxes during the excited state decay. Interestingly, and perhaps fortuitously, the time-dependent DFT-optimized exited-state geometry of Fe(2)(μ-S(2)C(3)H(6))(CO)(6) with a semibridging CO is reminiscent of the geometry of the Fe(2)S(2) subcluster of the active site observed in Fe-Fe hydrogenase X-ray crystal structures. We suggest these wavelength-dependent excitation dynamics could significantly alter potential mechanisms for light-driven catalysis.

De Novo design in organometallic chemistry: stabilizing iridium(V)

Abstract Modern density functional theory (DFT) calculations are well suited for designing and testing alternative ligand schemes for transition-metal organometallic complexes. DFT methods have been applied to a variety of ligand systems and substrates (alkanes and silane) for the reaction (η x -L)L′Ir III R+R′H⇔(η x -L)L′Ir V RR′H (η x -L=Cp R , Tp, and carborane; L′=PR 3 , CR 3 − , SiR 3 − , and SnR 3 − ; R=CH 3 , H; R′=Aryl, CR 3 , and H) with the goal of finding ligand–substrate combinations that will stabilize the Ir(V) species. This species is of particular interest, as it is the putative intermediate in the CH bond activation by Ir(III) complexes. Among the donor ligands examined were various multihapto ligands (η x -L), alternative phosphines, anionic silanes (SiR 3 − ) and stannanes (SnR 3 − ), and chelating ligands. Cationic Ir(V) intermediates produced by oxidative addition of an alkane are not easily stabilized when compared with their Ir(III) counterparts. Replacing the phosphine donor ligands with more covalent inorganic ligands, specifically silyl and stannyl ligands (AR 3 ), produces neutral Ir(V) complexes that are more stable than the Ir(III) reactants but would be subject to alkane elimination except at very low temperatures. Reacting the unsaturated 16 e − species [CpIr III PR 3 LR 3 ] + (where R=H, CH 3 and L=C, Si) with the appropriate amount of silane (HSiR′ 3 ) might also afford Ir(V) complexes [CpIr V PR 3 LR 3 SiR′ 3 H] + that are stable enough to be observed spectroscopically, and in some instances, possibly isolated.

The multiple equilibrium analysis quantitative prediction of single and multi-component adsorption isotherms on carbonaceous and zeolitic solids

Abstract The previously introduced multiple equilibrium analysis (MEA), which produces equilibrium constants ( K i ), capacities ( n i ), and thermodynamic parameters (enthalpies, Δ H i , and entropies, Δ S i ) of adsorption for each process, has been used to predict adsorption isotherms for N 2 , CO, CH 4 , C 2 H 6 , and SF 6 on one zeolitic (HZSM-5) and five carbonaceous (A-572, A-563, A-600, F-300, and BPL) solids. The adsorption of CO is best reproduced on each of the solids. In general, the adsorption of N 2 has been accurately predicted, while CH 4 and C 2 H 6 are underpredicted and SF 6 is overpredicted. Previously reported high-pressure data for the adsorption of CH 4 on BPL was very accurately predicted. The application of the MEA prediction of adsorption behavior has quite a potential for a variety of applications. Adsorbents can be used for catalyst supports, gas separation, respiratory protection, environmental applications, and even have the potential for fuel storage capabilities. The prediction of adsorption performance will lead to a greater understanding of the fundamental interactions involved in these systems and will help create new and better systems.

Phosphoryl transfers of the phospholipase D superfamily: a quantum mechanical theoretical study.

The HKD-containing Phospholipase D superfamily catalyzes the cleavage of the headgroup of phosphatidylcholine to produce phosphatidic acid and choline. The mechanism of this cleavage process is studied theoretically. The geometric basis of our models is the X-ray crystal structure of the five-coordinate phosphohistidine intermediate from Streptomyces sp . Strain PMF (PDB Code = 1V0Y ). Hybrid ONIOM QM:QM methodology with Density Functional Theory (DFT) and semiempirical PM6 (DFT:PM6) is used to acquire thermodynamic and kinetic data for the initial phosphoryl transfer, subsequent hydrolysis, and finally, the formation of the experimentally observed ″dead-end″ phosphohistidine product (PDB Code = 1V0W ). The model contains nineteen amino acid residues (including the two highly conserved HKD-motifs), four explicit water molecules, and the substrate. Via computations, the persistence of the short-lived five-coordinate phosphorane intermediate on the minutes times scale is rationalized. This five-coordinate phosphohistidine intermediate energetically exists between the hydrolysis event and ″substrate reorganization″ (the reorganization of the in vitro model substrate within the active site). Computations directly support the thermodynamic favorability of the in vitro four-coordinate phosphohistidine product. In vivo, the activation energy of substrate reorganization is too high, perhaps due to a combination of substrate immobility when embedded in the lipid bilayer, as well as its larger steric bulk compared to the compound used in the in vitro substrate soaks. On this longer time scale, the enzyme will migrate along the lipid membrane toward its next substrate target, rather than promote the formation of the dead-end product.

Time-resolved infrared studies of a trimethylphosphine model derivative of [FeFe]-hydrogenase.

Model compounds that structurally mimic the hydrogen-producing active site of [FeFe]-hydrogenases have been studied to explore potential ground-state electronic structure effects on reaction mechanisms compared to hexacarbonyl derivatives. The time-dependent behavior of Fe2(μ-S2C3H6)(CO)4(PMe)2 (A) in room temperature n-heptane and acetonitrile solutions was examined using various ultrafast UV and visible excitation pulses with broadband IR-probe spectroscopy of the carbonyl (CO) stretching region. Ground- and excited-state electronic and CO-stretching mode vibrational properties of the possible isomers of A were also examined using density functional theory (DFT) computations. In n-heptane, 355 and 532 nm excitation resulted in short-lived (135 ± 74 ps) bands assigned to excited-state, CO-loss photoproducts. These bands decay away, forming new long-lived absorptions that are likely a mixture of isomers of both three-CO and four-CO ground-state isomers. These new bands grow in with a time scale of 214 ± 119 ps and persist for more than 100 ns. In acetonitrile, similar results are seen with a 532 nm pump, but the 355 nm data lack evidence of the longer-lived bands. In either solvent, the 266 nm pump data seem to also lack longer-lived bands, but the intensities are significantly lower in this data, making firm conclusions more difficult. We suggest that these wavelength-dependent excitation dynamics significantly alter potential mechanisms and efficiencies for light-driven catalysis.

Factors affecting the structure of substituted tris(pyrazolyl)borate rhodium dicarbonyl complexes

Predictions by density functional calculations of the structure and relative energy of various isomers of the hydridotris(pyrazol-1-yl)borate ligand in Tp3R,5R rhodium(I) dicarbonyl complexes (R=H, Me) and their IR and 11B NMR spectra are compared to experimental observations. The lowest energy structure of Tp3,5-Me-, Tp3-Me-, and TpRh(CO)2 is a non-classical square pyramidal (SPy) structure with a long metal apical ligand distance in rapid exchange with an equivalent SPy structure through a low energy trigonal bipyramid (TBP) transition state (a ‘reverse’ Berry pseudorotation). A second higher energy minimum, a pseudo square-planar complex with the third uncoordinated pyrazolyl arm rotated approximately parallel with the metal ligand pseudo-plane (SP1), is accessed through a second low energy transition state. Another pseudo square-planar minimum structure (SP2) is produced by a transition state, which lengthens the rhodium-apical nitrogen (of the third pyrazolyl arm) bond distance. The relative stability of SP2 depends on the degree of tris(pyrazolyl)borate (Tp) substitution, where 5-substituents larger than hydrogen disfavor SP2 because of steric interactions. The previously reported empirical correlation between 11B NMR chemical shifts, νBH stretching frequencies, and the crystallographic Tp ligand denticity is reproduced by our calculations. The variety of structures observed by experiment can be explained by the calculated relative energies of the structures, the bulk dielectric of the solvents when in solution, specific interaction by certain solvents, and conditions of crystallization when in the solid-state.