Victor G. Young

University of Minnesota Duluth, Duluth, Minnesota, United States

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Publications (231)1097.32 Total impact

  • Ibrahim A Alfurayj · Victor G Young · Michael P Jensen
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    ABSTRACT: Consecutive thermochromic lattice distortional and spin crossover equilibria in solid-state Ni(detu)4Cl2 (detu = N,N'-diethylthiourea) are investigated by variable-temperature X-ray crystallography (173-333 K), DFT calculations, and differential scanning calorimetry. Thermochromism and anomalous magnetism were reported previously (S. L. Holt, Jr., et al. J. Am. Chem. Soc. 1964, 86, 519-520); the latter was attributed to equilibration of a singlet ground state and a thermally accessible triplet state, but structural data were not obtained. A crystal structure at 173(2) K revealed [Ni(detu)4](2+) centers with distorted planar ligation of nickel(II) to the four sulfur atoms, with an average Ni-S bond length of 2.226(3) Å. The nickel ion was displaced out-of-plane by 0.334 Å toward a proximal apical chloride at a nonbonding distance of 3.134(1) Å. Asymmetry in the trans S-Ni-S angles was coupled to a monoclinic ↔ tetragonal lattice distortion (T1/2 = 254 ± 11 K), resulting in thermochromism. Spin crossover occurs by tetragonal modulation of nickel(II) with approach of the proximal chloride at higher temperatures (T1/2 = 383 ± 18 K), which is consistent with a contraction of -0.096(4) Å in the Ni···Cl separation observed at 293 K. A high-spin (S = 1) square-pyramidal [Ni(dmtu)4Cl](+) model (dmtu = N,N'-dimethylthiourea) was optimized by DFT calculations, which estimated limiting equatorial Ni-S bond lengths of 2.45 Å and an apical Ni-Cl bond of 2.43 Å. Electronic spectra of the spin isomers were calculated by TD-DFT methods. Assignment of the FTIR spectrum was assisted by frequency calculations and isotope substitution.
    No preview · Article · Feb 2016 · Inorganic Chemistry
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    ABSTRACT: The structural properties of a series of scandium inorganic acid derivatives were determined. The reaction of Sc(0) 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(κ(2)-NO3)(μ-OH)]NO3}2 (2a), [(H2O)4Sc(κ(2)-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 (45)Sc nuclear magnetic resonance spectroscopic studies.
    No preview · Article · Dec 2015 · Inorganic Chemistry
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    ABSTRACT: Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula "(py3tren)CoCu" (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc(+)/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co-Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)(+4) state via a Co-Cu σ bond that is weakened by partial population of the Co-Cu σ antibonding orbital. By contrast, no covalent Co-Cu bonding is predicted for the (CoCu)(+3) analogue, and the d-electrons are fully localized at individual metals.
    No preview · Article · Nov 2015 · Inorganic Chemistry
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    ABSTRACT: The title compounds, (N-methyl-N-phenyl­amino)(N-methyl-N-phenyl­car­bam­oyl)sulfide, C15H16N2OS, (I), and (N-methyl-N-phenyl­amino)­(N-methyl-N-phenyl­carbamo­yl)disulfane, C15H16N2OS2, (II), are stable derivatives of (chloro­carbon­yl)sulfenyl chloride and (chloro­carbon­yl)disulfanyl chloride, respectively. The torsion angle about the S—S bond in (II) is −92.62 (6)°, which is close to the theoretical value of 90°. In the crystal of (II), non-classical inter­molecular C—H⋯O hydrogen bonds form centrosymmetric cyclic dimers [graph set R 2 2(10)], while inter-dimer C—H⋯S inter­actions generate chains extending along the b axis.
    Preview · Article · Nov 2015
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    Preview · Dataset · Oct 2015
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    Preview · Dataset · Oct 2015
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    Preview · Dataset · Oct 2015
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    ABSTRACT: The title compound, C 6 H 11 NO 3 S, provides entries to novel carbamoyl disulfanes and related compounds of interest to our laboratory. The atoms of the central O(C=S)N(C=O)O fragment have an r.m.s. deviation of 0.1077 Å from the respective least-squares plane. While several conformational orientations are conceivable, the crystal structure shows only the one in which the carbonyl and the thiocarbonyl moieties are anti to each other across the central conjugated C—N—C moiety. Pairs of 2.54 Å N—H...S=C hydrogen bonds between adjacent molecules form centrosymmetric dimers in the crystal.
    No preview · Article · Oct 2015
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    ABSTRACT: The title compound, C14H16N2S3, crystallized with two independent mol­ecules [(1 a) and (1 b)] in the asymmetric unit. Both mol­ecules display a pseudo-trans conformation. The two consecutive S—S bond lengths of the tris­ulfane unit of mol­ecule (1 a) are 2.06 (3) and 2.08 (3) Å, and 2.08 (3) and 2.07 (2) Å for mol­ecule (1 b). Torsion angles about each of the two S—S bonds are 86.6 (2) and 87.0 (2)° for (1 a), and −84.6 (2) and −85.9 (2)° for (1 b). The core atoms, viz. the N—S—S—S—N moiety, of the two mol­ecules superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enanti­omers. In mol­ecule (1 a), the two phenyl rings are inclined to one another by 86.7 (3)°, and in mol­ecule (1 b), by 81.1 (3)°. In the crystal, mol­ecules are linked via C—H⋯π inter­actions, forming sheets lying parallel to (010).
    Preview · Article · Jul 2015
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    ABSTRACT: Raman spectroscopy is a powerful method for identifying ion-ion interactions, but only if the vibrational band signature for the anion coordination modes can be accurately deciphered. The present study characterizes the PF6- anion P-F Raman symmetric stretching vibrational band for evaluating the PF6-...Li+ cation interactions within LiPF6 crystalline solvates to create a characterization tool for liquid electrolytes. To facilitate this, the crystal structures for two new solvates—(G3)1:LiPF6 and (DEC)2:LiPF6 with triglyme and diethyl carbonate, respectively—are reported. The information obtained from this analysis provides key guidance about the ionic association information which may be obtained from a Raman spectroscopic evaluation of electrolytes containing the LiPF6 salt and aprotic solvents. Of particular note is the overlap of the Raman bands for both solvent-separated ion pair (SSIP) and contact ion pair (CIP) coordination in which the PF6- anions are uncoordinated or coordinated to a single Li+ cation, respectively.
    No preview · Article · Apr 2015 · The Journal of Physical Chemistry C
  • Jessica H. Urbelis · Victor G. Young · Jennifer A. Swift
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    ABSTRACT: Co-crystallization of the high energy material CL-20 and triphenylphosphine oxide yields a 1:2 cocrystal in which CL-20 molecules adopt two different low energy conformations. Hydrogen bonding interactions between the H atoms on the isowurtzitane cage and phosphine oxide are consistent with solvent effects seen in previous crystal growth studies.
    No preview · Article · Jan 2015 · CrystEngComm
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    ABSTRACT: Pseudotetrahedral scorpionato halide complexes [(TpPh,Me)Ni–X] [TpPh,Me = hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate] were synthesized by metathesis of Tl(TpPh,Me) and NiX2 (X = Cl, Br, I). Pyrazole adducts [(TpPh,Me)Ni(HpzPh,Me)(X)] (X = Cl, I) were also obtained. [(TpPh,Me)Ni–X] (X = Br, I) are isomorphous with previously reported [(TpPh,Me)Ni–Cl], and a new solvated pseudo-polymorph [(TpPh,Me)Ni–Cl]·2CH2Cl2 was found in this work. Ni–X bond lengths correspond to ionic radii of the halide ions, but some variations in Ni–Cl and Ni–N bond lengths are respectively attributed to bending of the chloride from the ideal threefold HB···Ni axis and to the size of the 3-pyrazole substituents. Electronic spectra were rationalized by means of time-dependent (TD) DFT calculations on simplified C3v-symmetric [(Tp)Ni–X] models. Exogenous pyrazole binds to give the pentacoordinate adducts [(TpPh,Me)Ni(HpzPh,Me)(X)] (X = Cl, I). We obtained a crystal structure of the iodide adduct, as well as that of [(TpPh,Me)Ni(HpzPh,Me)(Cl)]·0.5MeCN, isomorphous with a previously reported aquo monosolvate. A hallmark of adduct formation is an intramolecular N–H···X hydrogen bond between the added pyrazole and the adjacent halide ligand, thus giving rise to a strong IR absorption band. The stretching frequency correlates to the N(H)···X separation for the range of known adducts.
    No preview · Article · Dec 2014 · Berichte der deutschen chemischen Gesellschaft
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    ABSTRACT: The synthesis and solid state structures of homo- and heteroleptic Zr and Ti complexes of 2-(diphenylphosphino)pyrrolide (NP) are reported. The homoleptic Zr(NP)4 (1) and Ti(NP)4 (2) are 8-coordinate in the solid state, and both show extremely long M-P bonds of approximately 2.9 Å. In solution, the phosphine ligands in all complexes are labile: in the titanium complexes phosphine dissociation is rapid at room temperature and equilibrates all phosphines into a single 31P resonance, whereas in the Zr complex 1 dissociation is slower and full equilibration does not occur until 90 °C. The potential to utilize these novel complexes as metalloligands toward other transition metals is discussed.
    No preview · Article · Dec 2014 · Polyhedron
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    ABSTRACT: Synthesis and characterization of several new pseudotetrahedral arylthiolate complexes [(Tp(Ph,Me))Ni-SAr] (Tp(Ph,Me) = hydrotris{3-phenyl-5-methyl-1-pyrazolyl}borate; Ar = Ph, 2,4,6-(i)Pr3C6H2, C6H4-4-Cl, C6H4-4-Me, C6H4-4-OMe) are reported, including X-ray crystal structures of the first two complexes. With prior results, two series of complexes are spanned, [(Tp(Ph,Me))Ni-S-2,4,6-RC6H2] (R'' = H, Me, (i)Pr) plus the xylyl analogue [(Tp(Ph,Me))Ni-S-2,6-Me2C6H3], as well as [(Tp(Ph,Me))Ni-S-C6H4-4-Y] (Y = Cl, H, Me, OMe), intended to elucidate steric and/or electronic effects on arylthiolate coordination. In contrast to [(Tp(Me,Me))Ni-SAr] analogues that adopt a sawhorse conformation, the ortho-disubstituted complexes show enhanced trigonal and Ni-S-Ar bending, reflecting the size of the 3-pyrazole substituents. Moreover, weakened scorpionate ligation is implied by spectroscopic data. Little spectroscopic effect is observed in the series of para-substituted complexes, suggesting the observed effects are primarily steric in origin. The relatively electron-rich and encumbered complex [(Tp(Ph,Me))Ni-S-2,4,6-(i)Pr3C6H2] behaves uniquely when dissolved in CH3CN, forming a square planar solvent adduct with a bidentate scorpionate ligand, [(κ(2)-Tp(Ph,Me))Ni(NCMe)(S-2,4,6-(i)Pr3C6H2)]. This adduct was isolated and characterized by X-ray crystallography. Single-point DFT and TD-DFT calculations on a simplified [(κ(2)-Tp)Ni(NCMe)(SPh)] model were used to clarify the electronic spectrum of the adduct, and to elucidate differences between Ni-SAr bonding and spectroscopy between pseudotetrahedral and square planar geometries.
    No preview · Article · Oct 2014 · Dalton Transactions
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    ABSTRACT: Cobalt-cobalt and iron-cobalt bonds are investigated in coordination complexes with formally mixed-valent [M2](3+) cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co2(DPhF)3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L(Ph)), the isolation of a dicobalt homobimetallic and an iron-cobalt heterobimetallic are demonstrated. The new [Co2](3+) and [FeCo](3+) cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal-metal bond distances of 2.29 Å for Co-Co and 2.18 Å for Fe-Co; the latter is the shortest distance for an iron-cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL(Ph) is more precisely described as (Fe0.94(1)Co0.06(1))(Co0.95(1)Fe0.05(1))L(Ph). The iron-cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe2(DPhF)3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M2](3+) cores are fully delocalized.
    Full-text · Article · Jul 2013 · Inorganic Chemistry
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    ABSTRACT: A new design strategy is described for chloride ion sensors based on suppression of excited state intramolecular proton transfer in squaramides as a fluorescence "turn on" mechanism.
    No preview · Article · Jan 2013 · Chemical Communications
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    ABSTRACT: Several electrically neutral, highly quadrupolar derivatives of the [closo-B10H10]2− cluster (I) substituted in the apical positions with onium fragments derived from 4-alkoxypyridine, 4-pentylthian, 4-pentylquinuclidine, or dinitrogen were synthesized from the parent cluster in 2–5 steps, and their thermal, structural, photophysical and dielectric properties were investigated. Only derivatives 2, containing thianium and alkoxypyridinium substituents with linear alkyl chains, exhibit liquid crystalline behavior and form a nematic phase. α-Branching of the alkoxy chain leads to marked destabilization of both crystalline and nematic phases, which suggests the importance of polar interactions in phase stabilization of these compounds. Derivatives 2 and 3 with one π and one σ substituent, Q+, exhibit a directional cluster-to-Q charge transfer and increase of the net electric dipole moment to μe = 17.9 D for 2a upon photo-excitation. They are weak fluorophores (Φf = 2–7%). Detailed investigation of 4-heptyloxypyridinium derivative 2b revealed that it exhibits a nematic phase above 100 °C with Δε = +1.3 (130 °C), and a moderate negative solvatochromism. Hyper-Rayleigh scattering measurement gave βHRS = 45 ± 10 × 10−30 esu at 1064 nm. In solutions, and presumably in the melt, it exists as a mixture of interconverting trans and cis isomers at about 4:1 ratio with ΔG298 = 0.82 ± 0.06 kcal mol−1 and ΔG‡298 = 25.3 ± 0.6 kcal mol−1 established by VT NMR methods.
    Full-text · Article · Jan 2013
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    ABSTRACT: 5,6-Dimethylbenzofurazan 1-oxide (Me2BF), C(8)H(8)N(2)O(2), occurs in four polymorphic forms that are polytypes of each other. Each polymorph of Me2BF contains molecules disordered about pseudo-twofold axes and arranged head-to-tail in ribbons, with the ribbons forming approximately planar layers held together by weak C-H...N and C-H...O interactions. Adjacent layers interact in different ways in the different polymorphs. In addition to twinning in the individual polymorphs, four examples of allotwining, that is, oriented overgrowths between different polymorphs, were found.
    No preview · Article · Oct 2012 · Acta crystallographica. Section B, Structural science
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    ABSTRACT: Reaction of two equivalents of K[1,3-(SiMe3)2C3H3] (= K[A′]) with MnCl2 in THF produces the allyl complex A′2Mn(thf)2; if the reaction is conducted in ether, the solvent-free heterometallic manganate species K2MnA′4 is isolated instead. With the related allyl K[1,1′,3-(SiMe3)3C3H2] (= K[A″]), reaction with MnCl2 in THF/TMEDA produces the corresponding adduct A″2Mn(tmeda). In the solid state, both A′2Mn(thf)2 and A″2Mn(tmeda) are monomeric complexes with σ-bonded allyl ligands (Mn–C = 2.174(2) and 2.189(2) Å, respectively). In contrast, K2MnA′4 is a two-dimensional coordination polymer, in which two of the allyl ligands on the Mn cation are σ-bonded (Mn–C = 2.197(6), 2.232(7) Å) and the third is π-bonded (Mn–C = 2.342(7)–2.477(7) Å). Both σ-allyls are π-coordinated to potassium cations, promoting the polymer in two directions; the π-allyl ligand is terminal. Density functional theory (DFT) calculations indicate that isolated high-spin (C3R2H3)2Mn (R = H, SiMe3) complexes would possess π-bound ligands. A mixed hapticity (π-allyl)(σ-allyl)MnE structure would result with the addition of either a neutral ligand (e.g., THF, MeCN) or one that is charged (Cl, H). Both allyl ligands in a bis(allyl)manganese complex are expected to adopt a σ-bonded mode if two THF ligands are added, as is experimentally observed in A′2Mn(thf)2. The geometry of allyl–Mn(II) bonding is readily modified; DFT results predict that [(C3H5)Mn]+ and (C3H5)MnCl should be σ-bonded, but the allyl in (C3H5)MnH is found to exhibit a symmetrical π-bonded arrangement. Some of this behavior is reminiscent of that found in bis(allyl)magnesium chemistry.
    No preview · Article · Aug 2012 · Organometallics
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    David K Ford · Victor G Young · George Barany
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    ABSTRACT: The title compound, C(4)H(6)O(2)S(4), was prepared by repeating, with subtle improvements, a multi-step route originally described by Mott & Barany [J. Chem. Soc. Perkin Trans. 1 (1984) ▶, pp. 2615-2621]. The title compound was obtained for the first time as a crystalline material. The two [(methyl-sulfan-yl)carbon-yl]sulfenyl moieties are essentially perpendic-ular to each other, each approximately planar (r.m.s. deviations of 0.02 and 0.01 Å) and with a C-S-S-C torsion angle = 90.99 (6)°, which compares well with the theoretical value of 90°.
    Preview · Article · Jul 2012 · Acta Crystallographica Section E Structure Reports Online

Publication Stats

6k Citations
1,097.32 Total Impact Points

Institutions

  • 1995-2015
    • University of Minnesota Duluth
      • Department of Chemistry and Biochemistry
      Duluth, Minnesota, United States
  • 1998-2014
    • University of Minnesota Twin Cities
      • Department of Chemistry
      Minneapolis, Minnesota, United States
    • Academy of Sciences of the Czech Republic
      Praha, Praha, Czech Republic
    • University of Michigan
      • Department of Chemistry
      Ann Arbor, Michigan, United States
  • 2011
    • University of Alberta
      • Department of Chemistry
      Edmonton, Alberta, Canada
  • 1996-2011
    • Saint Mary's University of Minnesota
      • Chemistry
      Minneapolis, Minnesota, United States
    • University of Guelph
      • Department of Chemistry
      XIA, Ontario, Canada
  • 2010
    • Lawrence University
      • Chemistry
      Lawrence, Kansas, United States
  • 1992-2010
    • Iowa State University
      • • Department of Chemistry
      • • Department of Materials Science and Engineering
      Ames, Iowa, United States
  • 2005
    • Stanford University
      • Department of Chemistry
      Palo Alto, California, United States
    • Dow Corning Corporation
      Seneffe, Walloon Region, United States
  • 2001-2004
    • University of Kansas
      • Department of Chemistry
      Lawrence, KS, United States
    • University of Wisconsin - Eau Claire
      Eau Claire, Wisconsin, United States
  • 2003
    • Ewha Womans University
      Sŏul, Seoul, South Korea
    • Stony Brook University
      • Department of Chemistry
      Stony Brook, New York, United States
  • 2000-2001
    • Arizona State University
      • Department of Chemistry and Biochemistry
      Mesa, AZ, United States
    • University of British Columbia - Vancouver
      • Department of Chemistry
      Vancouver, British Columbia, Canada
    • University of Barcelona
      Barcino, Catalonia, Spain
  • 1998-2000
    • Vanderbilt University
      • Department of Chemistry
      Nashville, MI, United States
  • 1997
    • University of Delaware
      • Department of Chemistry and Biochemistry
      Newark, DE, United States