A Prolific Catalyst for Dehydrogenation of Neat Formic Acid
Jeff Joseph A. Celaje, Zhiyao Lu, Elyse A. Kedzie, Nicholas J. Terrile, Jonathan N. Lo, and Travis J. Williams

Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

Celaje, J. A.; Lu, Z.; Kedzie, E. A.; Terrile, N. J.; Lo, J. N.; Williams, T. J. Nat. Commun. 2016, 7, 11308
DOI: 10.1038/ncomms11308

Dehydrogenation of Ammonia Borane through the Third Equivalent of Hydrogen
Xingyue Zhang, Lisa Kam, and Travis J. Williams

Ammonia borane (AB) has high hydrogen density (19.6 wt%), and can, in principle, release up to 3 equivalents of H2 under mild catalytic conditions. A limited number of catalysts are capable of non-hydrolytic dehydrogenation of AB beyond 2 equivalents of H2 under mild conditions, but none of these is shown directly to derivatise borazine, the product formed after 2 equivalents of H2 are released. We present here a high productivity ruthenium-based catalyst for non-hydrolytic AB dehydrogenation that is capable of borazine dehydrogenation, and thus exhibits among the highest H2 productivity reported to date for anhydrous AB dehydrogenation. At 1 mol% loading, (phen)Ru(OAc)2(CO)2 (1) effects AB dehydrogenation through 2.7 equivalents of H2 at 70 °C, is robust through multiple charges of AB, and is water and air stable. We further demonstrate that catalyst 1 has the ability both to dehydrogenate borazine in isolation and dehydrogenate AB itself. This is important, both because borazine derivatisation is productivity-limiting in AB dehydrogenation and because borazine is a fuel cell poison that is commonly released in H2 production from this medium.

Zhang, X.; Kam, L.; Williams, T. J. Dalton Trans. 2016, 45, 7672-7677
DOI: 10.1039/c6dt00604c

A Prolific Catalyst for Selective Conversion of Neat Glycerol to Lactic Acid
Zhiyao Lu, Ivan Demianets, Rasha Hamze, Nicholas J. Terrile, and Travis J. Williams

We report the synthesis and reactivity of a very robust iridium catalyst for glycerol to lactate conversion. The high reactivity and selectivity of this catalyst enable a sequence for the conversion of biodiesel waste stream to lactide monomers for the preparation of poly(lactic acid). Furthermore, experimental data collected with this system provide a general understanding of its reactive mechanism.

Lu, Z.; Demianets, I.; Hamze, R.; Terrile, N. J.; Williams, T. J. ACS Catal. 2016, 6, 2014-2017
DOI: 10.1021/acscatal.5b02732

Nitrogen-Based Ligands Accelerate Ammonia Borane Dehydrogenation with the Shvo Catalyst
Xingyue Zhang, Zhiyao Lu, Lena K. Foellmer, and Travis J. Williams

We previously reported that quantitative poisoning, a test for homogeneous catalysis, behaves oddly in the dehydrogenation of ammonia borane (AB) by Shvo’s catalyst, whereas the “poison” 1,10-phenanthroline (phen) accelerates catalysis and apparently prevents catalyst deactivation. Thus, we proposed a protective role for phen in the catalysis. Herein we account for the mechanistic origin of this accelerated AB dehydrogenation in the presence of phen and define the relevance boundaries of our prior proposal. In so doing, we present syntheses for novel amine- and pyridine-ligated homologues of the Shvo catalyst and show their catalytic efficacy in AB dehydrogenation. These catalysts are synthetically easy to access, air stable, and rapidly release over 2 equiv of H2. The mechanisms of these reactions are also discussed.

Zhang, X.; Lu, Z.; Lena, K. F.; Williams, T. J. Organometallics 2015, 34, 3732-3738
DOI: 10.1021/acs.organomet.5b00409

A (Fluoroalkyl)Guanidine Modulates the Relaxivity of a Phosphonate-Containing T1-Shortening Contrast Agent
Xinping Wu, Anna C. Dawsey, Buddhima N. Siriwardena-Mahanama, Matthew J. Allen, and Travis J. Williams

Responsive magnetic resonance imaging (MRI) contrast agents, those that change their relaxivity according to environmental stimuli, have promise as next generation imaging probes in medicine. While several of these are known based on covalent modification of the contrast agents, fewer are known based on controlling non-covalent interactions. We demonstrate here accentuated relaxivity of a T1-shortening contrast agent, Gd-DOTP5- based on non-covalent, hydrogen bonding of Gd-DOTP5- with a novel fluorous amphiphile. By contrast to the phosphonate-containing Gd-DOTP5- system, the relaxivity of the analogous clinically approved contrast agent,
Gd-DOTA- is unaffected by the same fluorous amphiphile under similar conditions.

Mechanistic studies show that placing the fluorous amphiphile in proximity of the gadolinium center in Gd-DOTP5- caused an increase in τm (bound-water residence lifetime or the inverse of water exchange rate, τm = 1/kex) and an increase in τR (rotational correlation time), with τR being the factor driving enhanced relaxivity. Further, these effects were not observed when Gd-DOTA- was treated with the same fluorous amphiphile. Thus, Gd-DOTP5- and Gd-DOTA- respond to the fluorous amphiphile differently, presumably because the former binds to the amphiphile with higher affinity. (DOTP = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraphosphonic acid; DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid).

Wu, X.; Dawsey, A. C.; Siriwardena-Mahanama, B. N.; Allen, M. J.; Williams, T. J. J. Fluor. Chem. 2014, 168, 177-183
DOI: 10.1016/j.jfluchem.2014.09.018

Control of Emission Colour with N-heterocyclic Carbene (NHC) Ligands in Phosphorescent Threecoordinate copper(I) Complexes
Valentina A. Krylova, Peter I. Djurovich, Brian L. Conley, Ralf Haiges, Matthew T. Whited, Travis J. Williams and Mark E. Thompson

A series of three phosphorescent mononuclear (NHC)–copper(I) complexes were prepared and characterized. Photophysical properties were found to be largely controlled by the NHC ligand chromophore. Variation of the NHC ligand leads to emission colour tuning over 200 nm range from blue to red, and emission efficiencies of 0.16–0.80 in the solid state.

Krylova, V. A.; Djurovich, P. I.; Conley, B. L.; Haiges, R.; Whited, M. T.; Williams, T. J.; Thompson, M. E. Chem. Commun. 2014, 50, 7176-7179
DOI: 10.1039/C4CC02037E

Synthesis, Structure, and Conformational Dynamics of Rhodium and Iridium Complexes of Dimethylbis(2-pyridyl)borate
Megan K. Pennington-Boggio, Brian L. Conley, Michael G. Richmond, and Travis J. Williams

Ring Flip

Rhodium(I) and Iridium(I) borate complexes of the structure [Me2B(2-py)2]ML2 (L2 = (tBuNC)2, (CO)2, (C2H4)2, cod, dppe) were prepared and structurally characterized (cod = 1,5-cyclooctadiene; dppe = 1,2-diphenylphosphinoethane). Each contains a boat-configured chelate ring that participates in a boat-to-boat ring flip. Computational evidence shows that the ring flip proceeds through a transition state that is near planarity about the chelate ring.

We observe an empirical, quantitative correlation between the barrier of this ring flip and the π acceptor ability of the ancillary ligand groups on the metal. The ring flip barrier correlates weakly to the Tolman and Lever ligand parameterization schemes, apparently because these combine both σ and π effects while we propose that the ring flip barrier is dominated by π bonding. This observation is consistent with metal-ligand π interactions becoming temporarily available only in the near-planar transition state of the chelate ring flip and not the boat-configured ground state. Thus, this is a first-of-class observation of metal-ligand π bonding governing conformational dynamics.

Pennington-Boggio, M. K.; Conley, B. L.; Richmond, M. G.; Williams, T. J. Polyhedron 2014, 84 24-31
DOI: 10.1016/j.poly.2014.05.042

Synthesis and Characterization of Dimethyldi(2-pyridyl)borate Nickel(II) Complexes: A Unimolecular Square Planar to Square Planar Rotation Around Nickel(II)
Jeff A. Celaje, Megan K. Pennington-Boggio, Robinson W. Flaig, Michael G. Richmond, and Travis J. Williams

Nickel(II) Rotation

The syntheses of novel dimethylbis(2-pyridyl)borate nickel(II) complexes 4 and 6 are reported. These complexes were unambiguously characterized by X-ray analysis. In dichloromethane solvent, complex 4 undergoes a unique square-planar to square-planar rotation around the nickel(II) center, for which activation parameters of ΔH = 12.2(1) kcal mol-1 and ΔS = 0.8(5) eu were measured via NMR inversion recovery experiments. Complex 4 was also observed to isomerize via a relatively slow ring flip: ΔH = 15.0(2) kcal mol-1; and ΔS = −4.2(7) eu. DFT studies support the experimentally measured rotation activation energy (cf. calculated ΔH = 11.1 kcal mol-1) as well as the presence of a high-energy triplet intermediate (ΔH = 8.8 kcal mol-1).

Celaje, J. A.; Pennington-Boggio, M. K.; Flaig, R. W.; Richmond, M. G.; Williams, T. J. Organometallics 2014, 33, 2019-2026
DOI: 10.1021/om500173j

Non-Covalent Self Assembly Controls the Relaxivity of Bound Gd Complexes
Vincent Li, Yoo-Jin Ghang, Richard J. Hooley, and Travis J. Williams


The relaxivity of a magnetically responsive Gd complex can be controlled by non-covalent molecular recognition with a water-soluble deep cavitand. Lowered relaxivity is conferred by a self-assembled micellar “off state”, and the contrast can be regenerated by addition of a superior guest.

Li, V.; Ghang, Y-J.; Hooley, R. J.; Williams, T. J. Chem. Commun. 2014, 50, 1375-1377
DOI: 10.1039/C3CC48389D

A Dual Site Catalyst for Mild, Selective Nitrile Reduction
Zhiyao Lu and Travis J. Williams

Mild Reduction of Nitriles

We report a novel ruthenium bis(pyrazolyl)borate scaffold that enables cooperative reduction reactivity in which boron and ruthenium centers work in concert to effect selective nitrile reduction. The pre-catalyst compound [κ3-(1-pz)2HB(N = CHCH3)] Ru(cymene)+ TfO- (pz = pyrazolyl) was synthesized using readily-available materials through a straightforward route, thus making it an appealing catalyst for a number of reactions.

Lu, Z.; Williams, T. J. Chem. Commun. 2014, 50, 5391-5393

A noncovalent, fluoroalkyl coating monomer for phosphonate-covered nanoparticles
Vincent Li, Andy Y. Chang, and Travis J. Williams

A noncovalent, fluoroalkyl coating monomer for phosphonate-covered nanoparticles

Gadolinium-containing phosphonate-coated gold nanoparticles were prepared and then non-covalently coated with an amphiphilic fluorous monomer. The monomer spontaneously self-assembles into a non-covalent monolayer shell around the particle. The binding of the shell utilizes a guanidinium–phosphonate interaction analogous to the one exploited by the Wender molecular transporter system. Particle–shell binding was characterized by a 27% decrease in 19F T1 of the fluorous shell upon exposure to the paramagnetic gadolinium in the particle and a corresponding increase in hydrodynamic diameter from 3 nm to 4 nm. Interestingly, a much smaller modulation of 19F T1 is observed when the shell monomer is treated with a phosphonate-free particle. By contrast, the phosphonate-free particle is a much more relaxive 1H T1 agent for water. Together, these observations show that the fluoroalkylguanidinium shell binds selectively to the phosphonate-covered particle. The system's relaxivity and selectivity give it potential for use in 19F based nanotheranostic agents.

Li, V.; Chang, A. Y.; Williams, T. J. Tetrahedron 2013, 69, 7741-7745

Introductory Chemistry: A Molar Relaxivity Experiment in the High School Classroom
Anna C. Dawsey, Kathryn L. Hathaway, Susie Kim and Travis J. Williams

Introductory Chemistry: A Molar Relaxivity Experiment in the High School Classroom

Dotarem and Magnevist, two clinically available magnetic resonance imaging (MRI) contrast agents, were assessed in a high school science classroom with respect to which is the better contrast agent. Magnevist, the more efficacious contrast agent, has negative side effects because its gadolinium center can escape from its ligand. However, Dotarem, though a less efficacious contrast agent, is a safer drug choice. After the experiment, students are confronted with the FDA warning on Magnevist, which enabled a discussion of drug efficacy versus safety. We describe a laboratory experiment in which NMR spin lattice relaxation rate measurements are used to quantify the relaxivities of the active ingredients of Dotarem and Magnevist. The spin lattice relaxation rate gives the average amount of time it takes the excited nucleus to relax back to the original state. Students learn by constructing molar relaxivity curves based on inversion recovery data sets that Magnevist is more relaxive than Dotarem. This experiment is suitable for any analytical chemistry laboratory with access to NMR.

Dawsey, A. C.; Hathaway, K. L.; Kim, S.; Williams, T. J. J. Chem. Educ. 2012, 90, 922-925

Alcohol Dehydrogenation with a Dual Site Ruthenium, Boron Catalyst Occurs at Ruthenium
Zhiyao Lu, Brock Malinoski, Ana Victoria Flores, Denver Guess, Brian L. Conley, and Travis J. Williams

The complex [(κ3-(N,N,O-py2B(Me)OH)Ru(NCMe)3]+ TfO- (1) is a catalyst for transfer dehydrogenation of alcohols, which was designed to function through a cooperative transition state in which reactivity was split between boron and ruthenium. We show here both stoichiometric and catalytic evidence to support that in the case of alcohol oxidation, the mechanism most likely involves reactivity only at the ruthenium center.

Lu, Z.; Malinoski, B.; Flores, A. V.; Guess, D.; Conley, B. L.; Williams, T. J. Catalysts 2012, 2, 412-421

A Three-Stage Mechanistic Model for Ammonia–Borane Dehydrogenation by Shvo’s Catalyst
Zhiyao Lu, Brian L. Conley, Travis J. Williams

A Three-Stage Mechanistic Model for Ammonia–Borane Dehydrogenation by Shvo’s Catalyst

We propose a mechanistic model for three-stage dehydrogenation of ammonia–borane (AB) catalyzed by Shvo’s cyclopentadienone-ligated ruthenium complex. We provide evidence for a plausible mechanism for catalyst deactivation and the transition from fast catalysis to slow catalysis and relate those findings to the invention of a second-generation catalyst that does not suffer from the same deactivation chemistry. The primary mechanism of catalyst deactivation is borazine-mediated hydroboration of the ruthenium species that is the active oxidant in the fast catalysis case. This transition is characterized by a change in the rate law for the reaction and changes in the apparent resting state of the catalyst. Also, in this slow catalysis situation, we see an additional intermediate in the sequence of boron, nitrogen species, aminodiborane. This occurs with concurrent generation of NH3, which itself does not strongly affect the rate of AB dehydrogenation.

Lu, Z.; Conley, B. L.; Williams, T. J. Organometallics 2012, 31, 6705-6714

A Ruthenium-Catalyzed Coupling of Alkynes with 1,3-Diketone
Megan K. Pennington-Boggio, Brian L. Conley, and Travis J. Williams

A Ruthenium-Catalyzed Coupling of Alkynes with 1,3-Diketone

Ruthenium(III) chloride hydrate is a convenient catalyst for the addition of active methylene compounds to aryl alkynes. These reactions are rapid, operationally simple, and high yielding in cases. Most significantly, no precautions are required to exclude air or water from the reactions. All reagents are commercially available at reasonable prices, and the reactions can be conducted in disposable glassware with minimal solvent.

Pennington-Boggio, M. K.; Conley, B. L.; Williams, T. J. J. Organometallic Chem. 2012, 716, 6-10
DOI: 10.1016/j.jorganchem.2012.05.017

Dual Site Catalysts for Hydride Manipulation
Brian L. Conley and Travis J. Williams

This comment describes our efforts to develop dual site catalysts for hydride manipulation. We began by analyzing the mechanism of alcohol oxidation with the ruthenium-based Shvo catalyst, which utilizes a proton transfer to template a hydride transfer from carbon to ruthenium in a single transition state. In our project we are working to extend this concept of reactivity from the use of proton transfer as a templating interaction for hydride transfer to the use of a Lewis acid to coordinate and direct a substrate to a metal. Along these lines, we have found that ammonia borane, a popular and high-weight-content hydrogen storage material, has been one of our best model substrates with which to study hydride transfer mechanisms. Our ongoing studies have thus far given new insight into the reactivity of the Shvo system, particularly regarding dehydrogenation of ammonia borane, and have enabled us to design a new, prolific, air- and water-tolerant, and reusable catalyst for ammonia borane dehydrogenation.

Conley, B. L.; Williams, T. J. Comments Inorg. Chem. 2012, 32, 195-218
DOI: 10.1080/02603594.2011.642087

Copper-Catalyzed Oxidation of Azolines to Azoles
Anna C. Dawsey, Vincent Li, Kimberly C. Hamilton, Jianmei Wang and Travis J. Williams

Copper Catalyzed Oxidation of Azolines to Azoles

We report herein convenient, aerobic conditions for the oxidation of thiazolines to thiazoles and data regarding the oxidation mechanism. These reactions feature operationally simple and environmentally benign conditions and proceed in good yield to afford the corresponding azoles, thus enabling the inexpensive preparation of valuable molecular building blocks. Incorporation of a novel diimine-ligated copper catalyst, [(MesDABMe)CuII(OH2)3]2+ [−OTf]2, provides increased reaction efficiency in many cases. In other cases copper-free conditions involving a stoichiometric quantity of base affords superior results.

Dawsey, A. C.; Li, V.; Hamilton, K. C.; Wang, J.; Williams, T. J. Dalton Trans. 2012, 41, 7994-8002
DOI: 10.1039/C2DT00025C

Synthesis and Phosphonate Binding of Guanidine-Functionalized Fluorinated Amphiphiles
Xinping Wu, Emine Boz, Amy M. Sirkis, Andy Y. Chang, Travis J. Williams

Synthesis of Fluorinated Amphiphile

We report herein convenient procedures for the use of highly fluorinated α,ω-diols (e.g. 1) as building blocks for the rapid assembly of amphiphilic materials containing a fluorous phase region. We describe expedient conversion of the parent diols to both symmetrically and asymmetrically substituted amphiphiles via the installation of an intermediate trifluoromethanesulfonyl ester. These sulfonate esters are versatile and easily manipulated intermediates, which can be readily converted to a variety of nitrogen, halogen, and carbon groups. Moreover, we show that for guanidine-terminated fluorous amphiphiles, these molecules can bind phosphonic acid groups in aqueous media. Thus, these materials offer a new strategy for decorating phosphorylated biomolecules with fluorine-rich coatings.

Wu, X.; Boz, E.; Sirkis, A. M.; Chang, A. Y.; Williams, T. J. J. Fluor. Chem. 2012, 135, 292-302
DOI: 10.1016/j.jfluchem.2011.12.011

A Robust, Air-Stable, Reusable Ruthenium Catalyst for Dehydrogenation of Ammonia Borane
Brian L. Conley, Denver Guess and Travis J. Williams

Dehydrogenation of Ammonia Borane

We describe an efficient homogeneous ruthenium catalyst for the dehydrogenation of ammonia borane (AB). This catalyst liberates more than 2 equiv of H2 and up to 4.6 system wt % H2 from concentrated AB suspensions under air. Importantly, this catalyst is robust, delivering several cycles of dehydrogenation at high [AB] without loss of catalytic activity, even with exposure to air and water.

Conley, B. L.; Williams, T. J. J. Am. Chem. Soc. 2011, 133, 14212-14215
DOI: 10.1021/ja2058154

An Inversion Recovery NMR Kinetics Experiment
Travis J. Williams, Allan D. Kershaw, Vincent Li and Xinping Wu

Inversion Recovery

A convenient laboratory experiment is described in which NMR magnetization transfer by inversion recovery is used to measure the kinetics and thermochemistry of amide bond rotation. The experiment utilizes Varian spectrometers with the VNMRJ 2.3 software, but can be easily adapted to any NMR platform. The procedures and sample data sets in this article will enable instructors to use inversion recovery as a laboratory activity in applied NMR classes and provide research students with a convenient template with which to acquire inversion recovery data on research samples.

Williams, T. J.; Kershaw, A. D.; Li, V.; Wu, X. J. Chem. Ed. 2011, 88, 665-669
DOI: 10.102/ed1006822

Dehydrogenation of Ammonia-borane by Shvo's Catalyst
Brian L. Conley and Travis J. Williams

Dehydrogenation of AB by Shvo's Catalyst

Shvo's cyclopentadienone-ligated ruthenium complex is an efficient catalyst for the liberation of exactly two molar equivalents of hydrogen from ammonia-borane, a prospective hydrogen storage medium. The mechanism for the dehydrogenation features a ruthenium hydride resting state from which dihydrogen loss is the rate-determining step.

Conley, B. L.; Williams, T. J. Chem. Commun. 2010, 46, 4815-4817

Thermochemistry and Molecular Structure of a Remarkable Agostic Interaction in a Heterobifunctional Ruthenium−Boron Complex
Brian L. Conley and Travis J. Williams

Conley Catalyst

A boron-pendant ruthenium species forms a unique agostic methyl bridge between the boron and ruthenium atoms in the presence of a ligating solvent, acetonitrile. NMR inversion−recovery experiments enabled the activation and equilibrium thermochemistry for formation of the agostic bridge to be measured. The mechanism for bridge formation involves displacement of an acetonitrile ligand; thus, this is a rare example of a case where an agostic C−H ligand competitively displaces another tightly binding ligand from a coordinatively saturated complex. Characterization of this complex gives unique insights into the development of C−H activation catalysis based on this ligand−metal bifunctional motif.

Conley, B. L.; Williams, T. J. J. Am. Chem. Soc. 2010, 132, 1764-1765
DOI: 10.1021/ja909858a

Discovery, Applications, and Catalytic Mechanisms of Shvo’s Catalyst
Brian L. Conley, Megan K. Pennington-Boggio, Emine Boz and Travis J. Williams

Shvo's Catalyst

Chem. Rev. 2010, 110 (4), 2294-2312

Mechanism of Hydride Abstraction by Cyclopentadienone-Ligated Carbonylmetal Complexes (M = Ru, Fe)
Megan K. Thorson, Kortney L. Klinkel, Jianmei Wang, Travis J. Williams

Mechanism of Hydride Abstraction

Cyclopentadienone-ligated ruthenium complexes, such as Shvo's catalyst, are known to oxidize reversibly alcohols to the corresponding carbonyl compounds. The mechanism of this reaction has been the subject of some controversy, but it is generally believed to proceed through concerted transfer of proton and hydride, respectively, to the cyclopentadienone ligand and the ruthenium center. In this paper we further study the hydride transfer process as an example of a coordinatively directed hydride abstraction by adding quantitative understanding to some features of this mechanism that are not well understood. We find that an oxidant as weak as acetone can be used to re-oxidize the intermediate ruthenium hydride without catalyst re-oxidation becoming rate-limiting. Furthermore, C–H cleavage is a significantly electrophilic event, as demonstrated by a Hammett reaction parameter of ρ = –0.89. We then describe how the application of our mechanistic insights obtained from the study have enabled us to extend the ligand-directed hydride abstraction strategy to include a rare example of an iron(0) oxidation catalyst.

European Journal of Inorganic Chemistry 2009, (2), 295-302