
Kyle A. GriceDePaul University · Department of Chemistry
Kyle A. Grice
PhD 2010, Univ of Washington
About
51
Publications
34,307
Reads
How we measure 'reads'
A 'read' is counted each time someone views a publication summary (such as the title, abstract, and list of authors), clicks on a figure, or views or downloads the full-text. Learn more
2,650
Citations
Introduction
Organometallic/Inorganic Chemist interested in activation and transformation of strong bonds (e.g. C-O, C-H), with specific goals of alkane functionalization and CO2 reduction. Really getting into bioinorganic chemistry as well!
See my website for more information:
sites.google.com/site/drkyleagrice/
Additional affiliations
Education
July 2005 - December 2010
August 2001 - May 2005
Harvey Mudd College, USA
Field of study
- Chemistry
Publications
Publications (51)
To understand the electrocatalytic CO2 reduction of metal carbonyl complexes without "non-innocent" ligands, the electrochemical responses of group 6 M(CO)6 (M = Cr, Mo, or W) and group 7 M2(CO)10 (M = Mn or Re) complexes were examined under Ar and CO2 at a glassy carbon electrode. All of the complexes showed changes in their cyclic voltammograms u...
Histone Deacetylase (HDAC) and similar proteins contain an active Zn-OH group and have been targets for inhibitors. Known inhibitors such as suberanilohydroxamic acid (SAHA), suberohydroxamic acid (SBHA), valproic acid, and 8-hydroxyquinoline (8-HQ) derivatives act on these enzymes by binding to the zinc center. To examine how these drugs interacte...
Air-stable L2PtMe2 complexes ligated by bulky aryl phosphite ligands were synthesized and characterized. The aryl phosphite ligands were prepared from substituted phenols and PCl3 or P(NMe2)3 without the use of an external base. The steric environment of the phenol controlled the number of substitutions at P(NMe2)3, resulting in selective formation...
Sodium borohydride (NaBH4) reacts with carbon dioxide (CO2) and bicarbonate (HCO3−) in aqueous solution to produce formate (HCO2−). Isotopic labeling experiments verified the product identity and illustrated that the carbon in the product originated from CO2/HCO3−. The addition of CO2 to borohydride resulted in formate production in isopropanol as...
Electrocatalytic properties, X-ray crystallographic studies, and infrared spectroelectrochemistry (IR-SEC) of Mn(bpy-tBu)(CO)Br and [Mn(bpy-tBu)(CO)(MeCN)](OTf) are reported. Addition of Brönsted acids to CO-saturated solutions of these Mn complexes and subsequent reduction of the complexes lead to the stable and efficient production of CO from CO....
Members of the Interactive Online Network of Inorganic Chemists (IONiC) report the development and sustained efforts to provide virtual professional development sessions: Supporting Learning with Interactive Teaching: a Hosted, Engaging Roundtable (SLiThEr). SLiThEr’s emerged from a community need at the start of the COVID-19 pandemic; since then,...
4-(tris(4-methyl-1H-pyrazol-1-yl)methyl)aniline was prepared in a 63% yield utilizing a C–F activation strategy from a mixture of 4-(trifluoromethyl)aniline, 4-methylpyrazole, and KOH in dimethylsulfoxide (DMSO). The identity of the product was confirmed by nuclear magnetic resonance spectroscopy, infrared spectroscopy, mass spectrometry, and singl...
Ni-catalyzed C-H functionalization reactions are becoming efficient routes to access a variety of functionalized arenes, yet the mechanisms of these catalytic C-C coupling reactions are not well understood. Here, we report the catalytic and stoichiometric arylation reactions of a nickel(II) metallacycle. Treatment of this species with silver(I)-ary...
Natural products and their analogs have been explored to stop the progression of cancer cells without unwanted side effects. Chalcones, compounds synthesized naturally in plants, have demonstrated potential as anti-cancer treatments. A library of bis-chalcones that are similar in structure to EF-24, a bis-chalcone molecule known to have anti-cancer...
Ni-catalyzed C-H functionalization reactions are becoming efficient routes to access a variety of functionalized arenes, yet the mechanisms of these catalytic C-C coupling reactions are not well understood. Here we report the catalytic and stoichiometric arylation reactions of a nickel(II) metallacycle. Treatment of this species with silver(I)-aryl...
Ni-catalyzed C-H functionalization reactions are becoming efficient routes to access a variety of functionalized arenes, yet the mechanisms of these catalytic C-C coupling reactions are not well understood. Here we report the catalytic and stoichiometric arylation reactions of a nickel(II) metallacycle. Treatment of this species with silver(I)-aryl...
Ni-catalyzed C-H functionalization reactions are becoming efficient routes to access a variety of functionalized arenes, yet the mechanisms of these catalytic C-C coupling reactions are not well understood. Here we report the catalytic and stoichiometric arylation reactions of a nickel(II) metallacycle. Treatment of this species with silver(I)-aryl...
Ni-catalyzed C-H functionalization reactions are becoming efficient routes to access a variety of functionalized arenes, yet the mechanisms of these catalytic C-C coupling reactions are not well understood. Here we report the catalytic and stoichiometric arylation reactions of a nickel(II) metallacycle. Treatment of this species with silver(I)-aryl...
A recently reported small natural product, 4-oxabicyclo[3.2.2]nona-1(7),5,8-triene, possesses a structure with a very strained geometry. In particular, the 3-atom bridge between para positions of an aromatic ring has no precedence in the literature. In this computational study, we herein report that the data for the surprising structure fits better...
Two new complexes, namely [Cu2(μ-2-nitrobenzoate)2(bpy)2(Cl)2]H2O (1) and [Cu2(μ-acetato)(phen)2(μ-OH)(μ-H2O](BF4)2 (2), where bpy = 2,2’-bipyridine and phen = 1,10-phenanthroline, were synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallized in the monoclinic crystal system with the space group P 21/n,...
The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C1-C
n
products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium trica...
Bipyridine ligands continue to be ubiquitous in coordination chemistry, and their use has grown exponentially in recent decades. New understanding of the their coordination and properties have been obtained, including leveraging redox non-innocence to enhance catalysis. What's more, new methods for synthesis of bipyridine ligands have been develope...
There is an urgent need to influence educational change in the methods by which science is taught. Numerous national agencies have called for science, technology, engineering, and mathematics (STEM) educational reform with recommendations to address retention and increase diversity of students in STEM disciplines. One way to address these recommend...
Molecular gold(I) and platinum(II) species were examined for the inhibition of liver fibrosis and the hepatitis C virus (HCV). Determination of inhibition efficiency was conducted via morphological analysis, cell viability, western blot analysis, and quantitative reverse transcription polymerase chain reaction (RT-PCR). Auranofin and Ph3PAuCl demon...
The electrocatalytic reduction of carbon dioxide (CO2) could be a powerful tool to generate chemical fuels and feedstock molecules relevant to the chemical industry. One of the major challenges for molecular catalysts remains the necessity of high overpotentials, which can be overcome by identifying novel routes that improve the energetic reaction...
The solution-phase structure and electronic relaxation dynamics of zinc bis-8-hydroxyquinoline [Zn(8HQ)2] in dimethylsulfoxide (DMSO) were examined using a broad array of spectroscopic techniques, complimented by ab initio calculations of molecular structure. The ground-state structure was determined using Extended X-Ray Absorption Fine Structure (...
Molecules based on the 5-arylthio-5H-chromenopyridine structure have been studied for a variety of medicinal applications, including liver fibrosis. We have recently found that the C-S linkage can be cleaved with Pt(II) and Au(I), something that was not previously recognized. In this current work, we examine the structure, properties, and reactivit...
A series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO2 reduction ability. The reported complexes are of the type Re(N-N)(CO)3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole...
Liver fibrosis is a critical wound healing response to chronic liver injury such as hepatitis C virus (HCV) infection. If persistent, liver fibrosis can lead to cirrhosis and hepatocellular carcinoma (HCC). The development of new therapies for preventing liver fibrosis and its progression to cancer associated with HCV infection remains a critical c...
The field of carbon dioxide reduction by homogeneous early transition complexes (groups 3–7) is reviewed. Many reactions with CO2 have been studied with late transition metal complexes (groups 8–10), and significant progress has been made in developing active and selective homogeneous catalysts for CO2 reduction with late metals. However, one major...
The electrochemical behaviors of seven early metal (groups 4?6) Cp2MCl2 species (M = Ti, Zr, Hf, V, Nb, Mo, and W; Cp = cyclopentadienyl) were examined under CO2 using cyclic voltammetry. In the presence of CO2, Cp2TiCl2, Cp2NbCl2, Cp2MoCl2 and Cp2WCl2 showed increases in current compared to an argon atmosphere at reductions corresponding to the fo...
The binding of drugs to metalloenzymes is an intricate process that involves several interactions, including binding of the drug to the enzyme active site metal, as well as multiple interactions between the drug and the enzyme residues. In order to determine the free energy contribution of Zn2+ binding by known metalloenzyme inhibitors without the...
Homogeneous electrocatalysts for CO 2 reduction have been explored by many groups. However, the focus has been on systems based on groups 7 or later in the periodic table. Recently, a few examples of catalytic CO 2 reduction have been observed at group 6 metals (Cr, Mo, and W) or earlier groups. Group 6 is notable as it is present in biological oxo...
PtII complexes containing unsymmetrical (pyridyl)pyrrolide ligands are shown to catalyze the hydroarylation of unactivated alkenes with selectivity for the anti-Markovnikov product. Substitution on the pyrrolide portion of the ligand allows effective tuning of the selectivity to anti-Markovnikov alkylarene products, whereas substitution on the pyri...
The thermolyses of ((tBu)P(O)N)PtMe2 (, (tBu)P(O)N = (di-tert-butylphosphinito)pyridine) and ((tBu)P(N-H)N)PtMe2 (, (tBu)P(N-H)N = (di-tert-butylphosphino)-2-aminopyridine) in benzene-d6 were investigated. With ((tBu)P(O)N)PtMe2, the product of a rollover cyclometalation of the pyridyl ring was observed in 80% yield along with formation of CH4. In...
[Pd(P(Ar)(tBu)2)2] (1, Ar=naphthyl) reacts with molecular oxygen to form PdII hydroxide dimers in which the naphthyl ring is cyclometalated and one equivalent of phosphine per palladium atom is released. This reaction involves the cleavage of both CH and OO bonds, two transformations central to catalytic aerobic oxidizations of hydrocarbons. Observ...
[Pd(P(Ar)(tBu)2)2] (1, Ar=naphthyl) reacts with molecular oxygen to form PdII hydroxide dimers in which the naphthyl ring is cyclometalated and one equivalent of phosphine per palladium atom is released. This reaction involves the cleavage of both CH and OO bonds, two transformations central to catalytic aerobic oxidizations of hydrocarbons. Observ...
The tetracarbonyl molybdenum and tungsten complexes of 2,2'-bipyridine and 4,4'-di-tert?-butyl-2,2'-bipyridine (M(bpy-R)(CO)?4; R = H, M = Mo (1), W (2); R = tBu, M = Mo (3), W (4)) are found to be active electrocatalysts for the reduction of CO2. The crystal structures of M(bpy-tBu)(CO)??4 (M = Mo (3), W (4)), the singly reduced complex [W(bpy)(CO...
Inhibition of histone deacetylase (HDAC) is known to induce tumor cell death, making it a promising approach for the treatment of cancer. To determine the energetic contribution of the active‐site Zn ²⁺ to HDAC interaction with inhibitors as superoylanilide hydroxamic acid (SAHA), we have explored Zn ²⁺ chelators as functional mimetics of HDAC as a...
With the goal of improving previously reported Mn bipyridine electrocatalysts in terms of increased activity and reduced overpotential, a bulky bipyridine ligand, 6,6'-dimesityl-2,2'-bipyridine (mesbpy), was utilized to eliminate dimerization in the catalytic cycle. Synthesis, electrocatalytic properties, X-ray diffraction (XRD) studies, and infrar...
The eventual deployment of large-scale systems for the electrochemical reduction of carbon dioxide (CO2) to fuels and commodity chemicals depends on the development of stable, highly active, and selective catalysts. The fac-Re(bpy-R)(CO)3X system, originally reported three decades ago, is very efficient for CO2 reduction to carbon monoxide (CO) eve...
A complete mechanism for the proton-dependent electrocatalytic reduction of CO2 to CO by fac-Re(bpy)(CO)3Cl that is consistent with experimental observations has been developed using first principles quantum chemistry. Calculated one-electron reduction potentials, non-aqueous pKas, reaction free energies, and reaction barrier heights provide deep i...
The phosphanylbipyridine ligands 6-(diphenylphosphanyl)-4,4′-dimethyl-2,2′-bipyridine (PPh2-Me2-bipy, a), 4,4′-di-tert-butyl-6-(diphenylphosphanyl)-2,2′-bipyridine (PPh2-tBu2-bipy, b), and 6-(diisopropylphosphanyl)-2,2′-bipyridine (PiPr2bipy, c) and the corresponding dinuclear copper complexes [Cu2(μ-PPh2-Me2-bipy)2(NCCH3)2](PF6)2 (1), [Cu2(μ-PPh2-...
Spectroscopic and structural comparisons are made between the rhenium anions with bpy-R ligands spanning a wide range of electron-withdrawing and donating abilities (R = CF3, H, Me, tBu, OMe). The synthesis and characterization of the rhenium anions [Re(bpy-R)(CO)(3)](-1) (bpy-R = 4,4'-disubstitued-2,2'-bipyridine; R = CF3, Me, OMe) are reported. T...
[Re(bpy-tBu)(CO)4](OTf) (bpy-tBu = 4,4'-di-tert-butyl-2,2'-bipyridine, OTf = trifluoromethanesulfonate) () and [Re(bpy)(CO)4](OTf) (bpy = 2,2'-bipyridine) () were synthesized and studied as proposed intermediates in the electrocatalytic reduction of carbon dioxide (CO2) by Re(bpy-R)(CO)3X. Both compounds demonstrated increased current responses in...
Where are the electrons that allow a highly reduced rhenium bipyridyl catalyst to attack CO2 , but not H(+) ? XAS and computational quantum chemistry indicate that the negative charge in [Re(bpy)(CO)3 ](-) and [Re(bpy-tBu)(CO)3 ](-) is not stored in a localized Re 5d state, but rather in the bipyridine ligand . The active states of this family of c...
The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein
we report stopped-flow UV-visible (UV-vis) spectroscopy, X-ray crystallographic, density functional theory (DFT), and electrochemical
kinetic studies of the Re(bipy-tBu)(CO)3(L) catalyst for the reduction of CO2 to CO. A re...
Two 1,5-diaza-3,7-diphosphacyclooctane (P2N2) ligands with alkyl-substituted phosphines have been synthesized via a versatile method that allows for improved control of the phosphine substituent. The methyl- and benzyl-substituted phosphine P2N2 ligands (PMe2NPh2 and PBn2NPh2) were synthesized and characterized by 31P1H NMR, 1H NMR, and elemental a...
Octahedral organometallic platinum(IV) complexes have been known for more than a century. Mechanistic studies suggest that
many reactions of these six-coordinate platinum(IV) complexes proceed through unobservable five-coordinate platinum(IV) intermediates.
Only recently have five-coordinate platinum(IV) complexes been isolated and characterized. T...
The bulky phosphine ligands di-tert-butyl(1-naphthyl)phosphine (1) or di-tert-butyl(N-indolyl)phosphine (2) react at room temperature with [(μ-SMe2)PtMe2]2. Coordination of the phosphine and C–H bond activation at an sp2 carbon of the ligand with the release of methane takes place to form the PC cyclometalated products [(PC)PtMe(SMe2)] (3 or 4, res...
The platinum(II) complex (PN)PtMe2 (1; PN = 2-((di-tert-butylphosphino)methyl)pyridine) reacts with molecular oxygen in benzene or methylene chloride solutions to form (PN)PtMe(OOMe) (2), a platinum(II) methylperoxo complex. The structure of the methylperoxo species 2 was determined by X-ray crystallography.
The platinum(IV) hydroxide and methoxide complexes fac-(dppbz)PtMe3(OR) (dppbz = o-bis(diphenylphosphino)benzene; R = H (1), CH3 (2)) have been prepared and characterized. Thermolysis of hydroxide 1 produces (dppbz)PtMe2 (3) and methanol in a rare example of directly observed sp3 carbon−oxygen reductive elimination from a metal center to form an al...
Questions
Questions (2)