Publications

Corbin, William C.; Cieslewski, Grzegorz C.; Hess, Ryan F.; Klamm, Bonnie E.; Goldfarb, Lauren G.; Boyle, Timothy J.; Yelton, William G.; Cashion, Avery T.

Abstract not provided.

Hess, Ryan F.; Klamm, Bonnie E.; Goldfarb, Lauren G.; Corbin, William C.; Boyle, Timothy J.; Yelton, William G.; Cashion, Avery T.

Abstract not provided.

Kemp, Richard K.; Perales, Diana P.; Wyss, Kevin M.; Sears, Jeremiah M.; Boyle, Timothy J.; Dickie, Diane U.

Abstract not provided.

Hess, Ryan F.; Corbin, William C.; Cashion, Avery T.; Cieslewski, Grzegorz C.; Klamm, Bonnie E.; Goldfarb, Lauren G.; Boyle, Timothy J.; Yelton, William G.

Abstract not provided.

Corbin, William C.; Cieslewski, Grzegorz C.; Hess, Ryan F.; Klamm, Bonnie E.; Boyle, Timothy J.; Yelton, William G.; Cashion, Avery T.

Abstract not provided.

Cook, Adam W.; DiAntonio, Christopher D.; Boyle, Timothy J.; Bell, Nelson S.; Keicher, David M.; Reinholtz, William D.; Chavez, Tom C.

Abstract not provided.

Dalton Transactions

Treadwell, LaRico J.; Boyle, Timothy J.; Phelan, W.A.; Parkes, Marie V.; Young, David P.

A series of nickel(ii) aryloxide ([Ni(OAr)2(py)x]) precursors was synthesized from an amide-alcohol exchange using [Ni(NR2)2] in the presence of pyridine (py). The H-OAr selected were the mono- and di-ortho-substituted 2-alkyl phenols: alkyl = methyl (H-oMP), iso-propyl (H-oPP), tert-butyl (H-oBP) and 2,6-di-alkyl phenols (alkyl = di-iso-propyl (H-DIP), di-tert-butyl (H-DBP), di-phenyl (H-DPhP)). The crystalline products were solved as solvated monomers and structurally characterized as [Ni(OAr)2(py)x], where x = 4: OAr = oMP (1), oPP (2); x = 3: OAr = oBP (3), DIP (4); x = 2: OAr = DBP (5), DPhP (6). The excited states (singlet or triplet) and various geometries of 1-6 were identified by experimental UV-vis and verified by computational modeling. Magnetic susceptibility of the representative compound 4 was fit to a Curie Weiss model that yielded a magnetic moment of 4.38(3)μB consistent with a Ni2+ center. Compounds 1 and 6 were selected for decomposition studied under solution precipitation routes since they represent the two extremes of coordination. The particle size and crystalline structure were characterized using transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). The materials isolated from 1 and 6 were found by TEM to form irregular shape nanomaterials (8-15 nm), which by PXRD were found to be Ni0 hcp (PDF: 01-089-7129) and fcc (PDF: 01-070-0989), respectively.

Casillas, Maddison C.; Fasulo, Francesca F.; Bell, Nelson S.; Boyle, Timothy J.; Treadwell, LaRico J.; Hernandez-Sanchez, Bernadette A.

Abstract not provided.

Hess, Ryan F.; Cieslewski, Grzegorz C.; Boyle, Timothy J.; Klamm, Bonnie E.; Goldfarb, Lauren G.; Stork, Isabella S.; Yelton, William G.

Abstract not provided.

Nguyen, Thao H.; Boyle, Timothy J.; Sears, Jeremiah M.; Treadwell, LaRico J.

Abstract not provided.

Sears, Jeremiah M.; Boyle, Timothy J.; Bell, Nelson S.; Cook, Adam W.; Treadwell, LaRico J.; Fasulo, Francesca F.; Hammel, Benjamin F.; linder, jesse l.; Nguyen, Thao H.

Abstract not provided.

Bell, Nelson S.; Sarobol, Pylin S.; Cook, Adam W.; Boyle, Timothy J.; Clem, Paul G.; Keicher, David M.; Hirschfeld, Deidre H.; Hall, Aaron C.

Abstract not provided.

Sears, Jeremiah M.; Boyle, Timothy J.; Hernandez-Sanchez, Bernadette A.; Nguyen, Thao H.; Casillas, Maddison C.

Abstract not provided.

Boyle, Timothy J.

Abstract not provided.

Hess, Ryan F.; Cieslewski, Grzegorz C.; Boyle, Timothy J.; Yelton, William G.; Klamm, Bonnie E.; Goldfarb, Lauren G.; Stork, Isabella N.

Abstract not provided.

Polyhedron

Boyle, Timothy J.; Neville, Michael L.; Parkes, Marie V.

A series of Group 4 phenoxy-thiols were developed from the reaction products of a series of metal tert-butoxides ([M(OBut)4]) with four equivalents of 4-mercaptophenol (H-4MP). The products were found by single crystal X-ray diffraction to adopt the general structure [(HOBut)(4MP)3M(μ-4MP)]2 [where M = Ti (1), Zr (2), Hf (3)] from toluene and [(py)2M(4MP)] where M = Ti (4), Zr (5) and [(py)(4MP)3Hf(μ-4MP)]2 (6) from pyridine (py). Varying the [Ti(OR)4] precursors (OR = iso-propoxide (OPri) or neo-pentoxide (ONep)) in toluene led to [(HOR)(4MP)3Ti(μ-4MP)]2 (OR = OPri (7), ONep (8)), which were structurally similar to 1. Lower stoichiometric reactions in toluene led to partial substitution by the 4MP ligands yielding [H][Ti(μ-4MP)(4MP)(ONep)3]2 (9). Independent of the stoichiometry, all of the Ti derivatives were found to be red in color, whereas the heavier congeners were colorless. Attempts to understand this phenomenon led to investigation with a series of varied -SH substituted phenols. From the reaction of H-2MP and H-3MP (2-mercaptophenol and 3-mercaptophenol, respectively), the isolated products had identical arrangements: [(ONep)2(2MP)Ti(μ,η2-2MP)]2 (10) and [(HOR)(3MP)M(μ-3MP)]2 (M/OR = Ti/ONep (11); Zr/OBut (12)) with a similar red color. Based on the simulated and observed UV-Vis spectra, it was reasoned that the color was generated due to a ligand-to-metal charge transfer for Ti that was not available for the larger congeners.

Journal of Coordination Chemistry

Boyle, Timothy J.; Sivonxay, Eric S.

The reaction of Group 4 metal alkoxides ([M(OR)4]) with the potentially bidentate ligand, 2-hydroxy-pyridine (2-HO-(NC5H4) or H-PyO), led to the isolation of a family of compounds. The products isolated from the reaction of [M(OR)4] [where M = Ti, Zr, or Hf; OR = OPri (OCH(CH3)2), OBut (OC(CH3)3), or ONep (OCH2C(CH3)3] under a variety of stoichiometries with H-PyO were identified by single crystal X-ray diffraction as [(OPri)2(PyO-κ2(O,N))Ti(μ-OPri)]2 (1), [(ONep)2Ti(μ(O)-PyO-κ2(O,N))2(μ-ONep)Ti(ONep)3] (2), [(ONep)2Ti(μ(O)-PyO-κ2(O,N))(η1(N),μ(O)-PyO)(μ-O)Ti(ONep)2]2 (2a), [H][(PyO-κ2(O,N))(η1(O)-PyO)Ti(ONep)3] (3), [(OR)2Zr(μ(O)-PyO-κ2(O,N))2(μ-OR)Zr(OR)3] (OR = OBut (4), ONep (5)), [(OR)2Zr(μ(O,N)-PyO-κ2(O,N))2(μ(O,N)-PyO)Zr(OR)3] (OR = OBut (6), ONep (7)), [[(OBut)2Zr(μ(O)-PyO-(κ2(N,O))(μ(O,N)-PyO)2Zr(OBut)](μ3-O)]2 (6a), [[(ONep)(PyO-κ2(N,O))Zr(μ(O,N)-PyO-κ2(N,O))2(μ(O)-PyO-κ2(N,O))Zr(ONep)](μ3-O)]2 (7a), [(OBut)(PyO-κ2(O,N))Zr(μ(O)-PyO-κ2(O,N))2((μ(O,N)-PyO)Zr(OBut)3] (8), [(OBut)2Hf(μ(O)-PyO-κ2(N,O))2(μ-OBut)Hf(OBut)3] (9), [(OR)2 M(μ(O)-PyO-κ2(N,O))2(μ(O,N)-PyO)M(OR)3] (OR = OBut (10), ONep (11)), and [(ONep)3Hf(μ-ONep)(η1(N),μ(O)-PyO)]2Hf(ONep)2 (12)·tol. The structural diversity of the binding modes of the PyO led to a number of novel structure types in comparison to other pyridine alkoxy derivatives. The majority of compounds adopt a dinuclear arrangement (1, 2, 4–11) but oxo-based tetra- (2a and 7a), tri- (12), and monomers (3) were observed as well. Compounds 1–12 were further characterized using a variety of analytical techniques including Fourier Transform Infrared Spectroscopy, elemental analysis, and multinuclear NMR spectroscopy.

Hess, Ryan F.; Boyle, Timothy J.; Lambert, Timothy N.; Kammler, Daniel K.; Small, Leo J.; Sears, Jeremiah M.

Abstract not provided.

Small, Leo J.; Hess, Ryan F.; Lambert, Timothy N.; Vigil, Julian A.; Boyle, Timothy J.; Sears, Jeremiah M.; Kelly, Maria K.

Abstract not provided.

Kemp, Richard K.; Greathouse, Jeffery A.; Boyle, Timothy J.

Abstract not provided.

Sears, Jeremiah M.; Boyle, Timothy J.; Hess, Ryan F.; Small, Leo J.

Abstract not provided.

ChemistrySelect

Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah M.; Cramer, Roger

A series of alkali metal yttrium neo-pentoxide ([AY(ONep)4]) compounds were developed as precursors to alkali yttrium oxide (AYO2) nanomaterials. The reaction of yttrium amide ([Y(NR2)3] where R=Si(CH3)3) with four equivalents of H-ONep followed by addition of [A(NR2)] (A=Li, Na, K) or Ao (Ao=Rb, Cs) led to the formation of a complex series of AnY(ONep)3+n species, crystallographically identified as [Y2Li3(μ3-ONep)(μ3-HONep)(μ-ONep)5(ONep)3(HONep)2] (1), [YNa2(μ3-ONep)4(ONep)]2 (2), {[Y2K3(μ3-ONep)3(μ-ONep)4(ONep)2(ηξ-tol)2][Y4K2(μ4-O)(μ3-ONep)8(ONep)4]•ηx-tol]} (3), [Y4K2(μ4-O)(μ3-ONep)8(ONep)4] (3 a), [Y2Rb3(μ4-ONep)3(μ-ONep)6] (4), and [Y2Cs4(μ6-O)(μ3-ONep)6(μ3-HONep)2(ONep)2(ηx-tol)4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 oC for 24 h). The final products after thermal processing were found by powder X-ray diffraction experiments to be Y2O3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.

Boyle, Timothy J.; Hess, Ryan F.; Lambert, Timothy N.; Small, Leo J.; Alam, Todd M.; Sears, Jeremiah M.; Yonemoto, Daniel T.; Fasulo, Francesca F.; Cramer, Roger C.; Neville, Michael L.

Abstract not provided.

RSC Advances

Small, Leo J.; Sears, Jeremiah M.; Lambert, Timothy N.; Boyle, Timothy J.; Hess, Ryan F.

The electroreduction of Er3+ in propylene carbonate, N,N-dimethylformamide, or a variety of quaternary ammonium ionic liquids (ILs) was investigated using [Er(OTf)3] and [Er(NTf2)3]. Systematic variation of the ILs' cation and anion, Er3+ salt, and electrode material revealed a disparity in electrochemical interactions not previously seen. For most ILs at a platinum electrode, cyclic voltammetry exhibits irreversible interactions between Er3+ salts and the electrode at potentials significantly less than the theoretical reduction potential for Er3+. Throughout all solvent-salt systems tested, a deposit could be formed on the electrode, though obtaining a high purity, crystalline Er0 deposit is challenging due to the extreme reactivity of the deposit and resulting chemical interactions, often resulting in the formation of a complex, amorphous solid-electrolyte interface that slowed deposition rates. Comparison of platinum, gold, nickel, and glassy carbon (GC) working electrodes revealed oxidation processes unique to the platinum surface. While no appreciable reduction current was observed on GC at the potentials investigated, deposits were seen on platinum, gold, and nickel electrodes.

Inorganic Chemistry

Boyle, Timothy J.; Sears, Jeremiah M.; Neville, Michael L.; Alam, Todd M.; Young, Victor G.

The structural properties of a series of scandium inorganic acid derivatives were determined. The reaction of Sc0 with concentrated aqueous hydrochloric acid led to the isolation of [(H2O)5Sc(Μ-OH)]24Cl·2H2O (1). Compound 1 was modified with a series of inorganic acids (i.e., HNO3, H3PO4, and H2SO4) at room temperature and found to form {[(H2O)4Sc(k2-NO3)(Μ-OH)]NO3}2 (2a), [(H2O)4Sc(k2-NO3)2]NO3·H2O (2b) (at reflux temperatures), {6[H][Sc(Μ-PO4)(PO4)]6}n (3), and [H][Sc(Μ3-SO4)2]·2H2O (4a). Additional organosulfonic acid derivatives were investigated, including tosylic acid (H-OTs) to yield {[(H2O)4Sc(OTs)2]OTs}·2H2O (4b) in H2O and [(DMSO)3Sc(OTs)3] (4c) in dimethyl sulfoxide and triflic acid (H-OTf) to form [Sc(H2O)8]OTf3 (4d). Other organic acid modifications of 1 were also investigated, and the final structures were determined to be {([(H2O)2Sc(Μ-OAc)2]Cl)6}n (5) from acetic acid (H-OAc) and [Sc(Μ-TFA)3Sc(Μ-TFA)3]n (6) from trifluoroacetic acid (H-TFA). In addition to single-crystal X-ray structures, the compounds were identified by solid-state and solution-state 45Sc nuclear magnetic resonance spectroscopic studies.