Gregory M Ferrence

Illinois State University, Нормальная, Illinois, United States

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Publications (111)370.14 Total impact

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    ABSTRACT: The structural adaptability of [V3O5(SeO3)3]n2n− layers in organically templated vanadium selenites was determined using a three step approach involving (i) an 84 reaction study with 14 distinct organic amines and 6 different reaction conditions, (ii) decision tree construction using both dependent and independent variables, and (iii) the derivation of chemical hypotheses. Formation of [V3O5(SeO3)3]n2n− layers requires that three criteria be met. First, compound stabilization through hydrogen-bonding with specific nucleophilic oxide ions is needed, requiring the presence of a primary ammonium site on the respective organic amine. Second, layer formation is facilitated through the use of compact ammonium cations that are able to achieve charge density matching with the anionic layers. Third, competition between organic ammonium cations and NH4+, which affects product formation, can be controlled through reagent choice and initial reactant concentrations. This approach to elucidate structural adaptability is generalizable and can be applied to a range of chemical systems.
    No preview · Article · Dec 2015 · Polyhedron
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    ABSTRACT: Two multinuclear complexes synthesized from Cu(NO 3 ) 2 and 6,6′-dihydroxybipyridine (dhbp) exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (6,6′-dihydroxybipyridine-2κ 2 N , N ′)[μ-6-(6-hydroxypyridin-2-yl)pyridin-2-olato-1:2κ 3 N , N ′: O 2 ](μ-hydroxido-1:2κ 2 O : O ′)(μ-nitrato-1:2κ 2 O : O ′)(nitrato-1κ O )dicopper(II), [Cu 2 (C 10 H 7 N 2 O 2 )(OH)(NO 3 ) 2 (C 10 H 8 N 2 O 2 )] or [Cu(6-OH-6′-O-bpy)(NO 3 )(μ-OH)(μ-NO 3 )Cu(6,6′-dhbp)], (I), with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water–ethanol mixture at neutral pH. The hexanuclear complex bis(μ 3 -bipyridine-2,2′-diolato-κ 3 O : N , N ′: O ′)tetrakis(6,6′-dihydroxybipyridine-κ 2 N , N ′)tetrakis(μ-hydroxido-κ 2 O : O ′)bis(methanol-κ O )tetrakis(μ-nitrato-κ 2 O : O ′)hexacopper(II), [Cu 6 (C 10 H 6 N 2 O 2 ) 2 (CH 4 O) 2 (OH) 4 (NO 3 ) 4 (C 10 H 8 N 2 O 2 ) 4 ] or [Cu(6,6′-dhbp)(μ-NO 3 ) 2 (μ-OH)Cu(6,6′-O-bpy)(μ-OH)Cu(6,6′dhbp)(CH 3 OH)] 2 , (II), with a 1:1 NO 3 –OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II) lies across an inversion center. Complexes (I) and (II) both display intramolecular O—H...O hydrogen bonding. Intermolecular O—H...O hydrogen bonding links symmetry-related molecules forming chains along [100] for complex (I) with π-stacking along [010] and [001]. Complex (II) forms intermolecular O—H...O hydrogen-bonded chains along [010] with π-stacking along [100] and [001].
    No preview · Article · Dec 2015
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    ABSTRACT: The hydrogen bonding ligand, 3-NH(t-butyl)-5-methyl-pyrazole, forms "scorpionate-like" first row transition metal complexes that are held together by hydrogen bonds rather than covalent bonds. The formulae of these complexes are (LH) n MX2, where n =3, 4; X=Cl, Br; and LH=3-NH(t-butyl)-5-methyl-pyrazole. The amino-substituted pyrazole can hydrogen bond via both the amino group and the pyrazole NH to form intramolecular NH to halide hydrogen bonds. These complexes have been well characterized and show a 3:1 ratio of ligand to metal for zinc and cobalt (1 and 2), and a 4:1 ratio of ligand to metal for manganese and nickel (3 and 4). The hydrogen bonding interactions appear to be stronger for the 3:1 complexes. The crystallographic and spectroscopic studies (EPR and NMR) have shown that these hydrogen-bonding interactions are strong enough to perturb metal halogen bond distances and, with non-hydrogen bonding solvents, the hydrogen bonds appear to hold these complexes together in solution.
    No preview · Article · Oct 2015 · Polyhedron
  • Timothy D Lash · Deyaa Isaac AbuSalim · Gregory M Ferrence
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    ABSTRACT: Base-catalyzed condensation of dicyclopentadienylmethane with a dipyrrylmethane dialdehyde gave a dicarbachlorin with an internal CH2 group. This unusual porphyrinoid retained highly diatropic characteristics and exhibited a porphyrin-like UV-vis spectrum.
    No preview · Article · Sep 2015 · Chemical Communications
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    ABSTRACT: Oxidation of tetraarylazuliporphyrins with silver(I) acetate in refluxing chloroform-acetonitrile afforded good yields of 21-oxyazuliporphyrins. Although hydroxyazuliporphyrin tautomers can be considered for this system, spectroscopic results and density functional theory calculations indicate that the keto form is favored, and this was confirmed by single-crystal X-ray diffraction. Oxyazuliporphyrins formally possess a 24π electron delocalization pathway, but the proton NMR spectra are consistent with macrocycles that have diatropic ring currents. Nucleus independent chemical shift and anisotropy of induced current density calculations also confirmed the diatropic nature of these macrocycles, although these results indicated that the seven-membered ring is antiaromatic. However, while the NMR spectra showed the azulene protons at atypically high field values, the results are consistent with a nonaromatic cycloheptatrienyl unit. Protonation gave dicationic products that exhibited enhanced diatropic character. Oxyazuliporphyrins readily form metalated derivatives with Ni(II), Pd(II), and Pt(II), and these complexes exhibited significant diatropic character even though the macrocycle is highly distorted. X-ray diffraction characterization of palladium(II) and platinum(II) complexes demonstrated that these derivatives are structurally virtually identical to a previously reported copper(II) oxyazuliporphyrin.
    No preview · Article · Sep 2015 · Inorganic Chemistry
  • Leah M. Stateman · Gregory M. Ferrence · Timothy D. Lash
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    ABSTRACT: The organometallic chemistry of azuliporphyrins has been extended to the first syntheses of rhodium(III) derivatives. Reaction of [Rh(CO)2Cl]2 with an azuliporphyrin in refluxing xylenes gave rhodium(III) azuliporphyrins in 62-67% yield. These derivatives incorporate solvent molecules as axial ligands and thereby introduce two carbon-rhodium bonds in a three-component reaction. The methylbenzyl ligands that are derived from xylenes overlie the π system of the porphyrinoid macrocycle, and proton NMR spectra show that these units are strongly shielded. The o-, m-, and p-xylene-derived complexes were characterized by X-ray crystallography, and this confirmed the presence of the central rhodium atom and the axial benzylic ligands. Additionally, when the azuliporphyrin was reacted with [Rh(CO)2Cl]2 in refluxing acetonitrile and then treated with acetone and basic alumina, a rhodium(III) azuliporphyrin with an acetone-derived axial ligand was generated. These results demonstrate that azuliporphyrins are superior organometallic ligands and therefore merit further investigation. (Chemical Equation Presented).
    No preview · Article · Aug 2015 · Organometallics
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    ABSTRACT: Initial synthetic efforts toward muironolide A based upon an intramolecular Diels-Alder strategy were hampered by a conjugate reduction rather than the desired half-reduction. An intermolecular Diels-Alder strategy was initiated that utilized electronically deactivated and sterically hindered dienes. The [4+2] cycloadditions were successful, but only with highly reactive dipolarophiles such as N-phenylmaleimide and 4-phenyl-1,2,4-triazoline-3,5-dione thus establishing the scope of these dienes. Although limited, installation of the α,β-unsaturated lactam embedded in the hexahydro-1H-isoindolinone is noteworthy.
    No preview · Article · Aug 2015 · Synthesis
  • Source
    Gregory M. Ferrence · Joshua L. Kocher
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    ABSTRACT: The title compound, C 7 H 14 N 2 Si, crystallizes in a tetragonal space group and exists as an N—H...N hydrogen-bonded tetramer, formed around the crystallographic fourfold rotoinversion axis. The molecular identity is clearly the 5-trimethylsilyl-3-methyl-1 H -pyrazole tautomer and the structure is isomorphous with that of 5- tert -butyl-3-methyl-1 H -pyrazole [Foces-Foces & Trofimenko (2001). Acta Cryst. E 57 , o32–o34].
    Preview · Article · Jun 2015
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    ABSTRACT: Structural differences in [V2Te2O10]n(2n-) chain metrics are directly ascribed to variations in noncovalent interactions in a series of organically templated vanadium tellurites, including [C6H17N3][V2Te2O10]·H2O, [C5H16N2][V2Te2O10], and [C4H14N2][V2Te2O10]. The noncovalent interaction (NCI) method was used to locate, quantify, and visualize intermolecular interactions in [C4H14N2][V2Te2O10] and [C5H16N2][V2Te2O10]. Variations in the van der Waals attractions between [1,4-diaminobutaneH2](2+) and [1,5-diaminopentaneH2](2+) result in divergent packing motifs for these cations, which causes a reorganization of N-H···O hydrogen bonding and variances in the [V2Te2O10]n(2n-) chain metrics. The application of the NCI method to this type of solid-state structure provides a direct method to elucidate the structural effects of weak noncovalent interactions.
    No preview · Article · Jan 2015 · Inorganic Chemistry
  • Stacy C Fosu · Gregory M Ferrence · Timothy D Lash
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    ABSTRACT: Dimethoxybenzitripyrranes were prepared in excellent yields by reacting benzene dicarbinols with BF3.Et2O and excess pyrrole in refluxing 1,2-dichloroethane. Reaction with a pyrrole dialdehyde in the presence of TFA, followed by oxidation with DDQ, afforded good yields of meso-diphenyldimethoxybenziporphyrins. These dimethoxyporphyrinoids exhibited weakly diatropic properties that were enhanced upon protonation. The dimethoxybenzitripyrranes also reacted with a thiophene dicarbinol to give dimethoxythiabenziporphyrins, and the nonplanar nature of this system was demonstrated by X-ray crystallography. The dimethoxybenziporphyrins reacted with palladium(II) acetate to give the related organometallic derivatives, but the thiabenziporphyrins underwent a demethylation to afford palladium(II) thiaoxybenziporphyrins. Related palladium(II) complexes were also prepared from previously reported thiacarbaporphyrinoids. The X-ray structure for one of the complexes showed that the six-membered ring is very distorted and the thiophene ring is strongly tilted out of the plane of the macrocycle. The dimethoxybenzitripyrranes also reacted with dimethoxybenzene dicarbinols to give the first examples of dibenziporphyrins, thereby further demonstrating the versatility of this synthetic methodology.
    No preview · Article · Oct 2014 · The Journal of Organic Chemistry
  • Deyaa I Abusalim · Gregory M Ferrence · Timothy D Lash
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    ABSTRACT: An adj-dicarbaporphyrin was prepared by carrying out a base-catalyzed MacDonald reaction between bis(3-indenyl)methane and a dipyrrylmethane dialdehyde. The porphyrinoid system exhibited highly diatropic characteristics and the proton NMR spectrum gave resonances at -5.74 and -6.24 ppm for the internal NH and CH protons, respectively. The UV-vis spectrum was also porphyrin-like, giving a Soret band at 455 nm and a series of Q bands at longer wavelengths. Addition of TFA gave a C-protonated monocation and at higher acid concentrations a dicationic species was observed. Addition of DBU afforded a mono-deprotonated porphyrinoid anion. All of these species retained highly diatropic characteristics. DFT calculations showed that a nonplanar tautomer with four internal hydrogens was favored, in agreement with the spectroscopic data. NICS calculations also confirmed the aromatic characteristics of the free base, cationic and anionic structures. The dicarbaporphyrin reacted with palladium(II) acetate in refluxing acetonitrile to give an unusual tripalladium sandwich complex. The complex consists of two dianionic palladium(II) dicarbaporphyrin units surrounding a palladium(IV) cation with unique η5-interactions that involve meso-carbon atoms.
    No preview · Article · Apr 2014 · Journal of the American Chemical Society
  • Ruoshi Li · Aaron D Lammer · Gregory M Ferrence · Timothy David Lash
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    ABSTRACT: Neo-confused porphyrins represent a unique family of porphyrin isomers that retain overall aromatic characteristics by virtue of a 17-atom 18pi electron delocalization pathway. These porphyrin analogues have a pyrrolic subunit connected in a 1,3-fashion so that a nitrogen atom is directly connected to a meso-bridging carbon. Pyrrole-3-carbaldehydes were shown to react with sodium hydride and 5-acetoxymethylpyrrole-2-carbaldehydes in DMF to give the crucial neo-confused dipyrrolic dialdehyde intermediates. MacDonald "2 + 2" condensation of the dialdehydes with a dipyrrylmethane afforded a dihydroporphyrinoid, and subsequent oxidation with 0.2% aqueous ferric chloride generated a series of fully conjugated neo-confused porphyrins. Unusual dihydroporphyrin by-products were also identified. Reaction of neo-confused porphyrins with nickel(II) or palladium(II) acetate in refluxing acetonitrile gave excellent yields of the corresponding organometallic derivatives. Proton NMR spectroscopy demonstrate that the diatropic character of this system is diminished compared to regular porphyrins, although neo-confused porphyrins retain porphyrin-like UV-vis spectra. Protonation led to the sequential formation of mono- and dicationic species. Proton NMR spectra for the dications showed the presence of enhanced diamagnetic ring currents.
    No preview · Article · Apr 2014 · The Journal of Organic Chemistry
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    ABSTRACT: The inclusion of Ln(III) ions into the 12-MC-4 framework generates the first heterotrimetallic complexes of this molecular class. The controllable and deliberate preparations of these compounds are demonstrated through 12 crystal structures of the Ln(III)M(I)(OAc)4[12-MCMn(III)(N)shi-4](H2O)4·6DMF complex, where OAc(-) is acetate, shi(3-) is salicylhydroximate, and DMF is N,N-dimethylformamide. Compounds 1-12 have M(I) as Na(I), and Ln(III) can be Pr(III) (1), Nd(III) (2), Sm(III) (3), Eu(III) (4), Gd(III) (5), Tb(III) (6), Dy(III) (7), Ho(III) (8), Er(III) (9), Tm(III) (10), Yb(III) (11), and Y(III) (12). An example with M(I) = K(I) and Ln(III) = Dy(III) is also reported (Dy(III)K(OAc)4[12-MCMn(III)(N)shi-4](DMF)4·DMF (14)). When La(III), Ce(III), or Lu(III) is used as the Ln(III) ions to prepare the Ln(III)Na(I)(OAc)4[12-MCMn(III)(N)shi-4] complex, the compound Na2(OAc)2[12-MCMn(III)(N)shi-4](DMF)6·2DMF·1.60H2O (13) results. For compounds 1-12, the identity of the Ln(III) ion affects the 12-MCMn(III)(N)shi-4 framework as the largest Ln(III), Pr(III), causes an expansion of the 12-MCMn(III)(N)shi-4 framework as demonstrated by the largest metallacrown cavity radius (0.58 Å for 1 to 0.54 Å for 11), and the Pr(III) causes the 12-MCMn(III)(N)shi-4 framework to be the most domed structure as evident in the largest average angle about the axial coordination of the ring Mn(III) ions (103.95° for 1 to 101.69° for 11). For 14, the substitution of K(I) for Na(I) does not significantly affect the 12-MCMn(III)(N)shi-4 framework as many of the structural parameters such as the metallacrown cavity radius (0.56 Å) fall within the range of compounds 1-12. However, the use of the larger K(I) ion does cause the 12-MCMn(III)(N)shi-4 framework to become more planar as evident in a smaller average angle about the axial coordination of the ring Mn(III) ions (101.35°) compared to the analogous Dy(III)/Na(I) (7) complex (102.40°). In addition to broadening the range of structures available through the metallacrown analogy, these complexes allow for the mixing and matching of a diverse range of metals that might permit the fine-tuning of molecular properties where one day they may be exploited as magnetic materials or luminescent agents.
    No preview · Article · Jan 2014 · Inorganic Chemistry
  • Source
    Timothy D Lash · Jessica A El-Beck · Gregory M Ferrence
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    ABSTRACT: A series of hetero-azuliporphyrins have been prepared by the "3 + 1" variant on the MacDonald condensation. Azulitripyrranes with tert-butyl and phenyl substituents reacted with thiophene or selenophene dialdehydes in the presence of TFA to give, following an oxidation step, thia- and selena-azuliporphyrins in 45-55% yield. Two of these compounds gave crystals suitable for X-ray crystallographic analysis and the data were consistent with the presence of a 17-atom delocalization pathway. The hetero-azuliporphyrins have significant diatropic character that is enhanced by the presence of an electron-donating tert-butyl substituent. The aromatic character is further increased in polar solvents such as DMSO, which are believed to stabilize dipolar resonance contributors with 18π electron delocalization pathways. Protonation also greatly increases the diatropic characteristics of these macrocycles. The porphyrinoids underwent an oxidative ring contraction with t-BuOOH-KOH to give moderate yields of benzoheterocarbaporphyrins. Reaction of azulitripyrranes with 2,5-furandicarbaldehyde afforded oxa-azuliporphyrins, a class of carbaporphyrinoids that had previously been inaccessible. These "missing links" in the study of heteroazuliporphyrins were isolated as the dihydrochloride salts. Protonated oxa-azuliporphyrins are stable aromatic compounds, but the free base forms underwent rapid decomposition in solution.
    Preview · Article · Nov 2013 · Organic & Biomolecular Chemistry
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    ABSTRACT: A set of formation principles governing organically templated vanadium selenite oxalates are described in the context of nine new compounds. The compositions of the reaction mixture dictate the form of the secondary building units from which [(VO)2(C2O4)(SeO3)2]n2n– layers are constructed. The strength of hydrogen-bonding interactions is maximized in these compounds, directly affecting the orientations of the organic ammonium cations and enabling amine packing efficiency to affect layer tessellation. The orientations of selenite stereoactive lone pairs are driven by the minimization of internal void space. Compound symmetry can be directed to chiral space groups through the use of chiral components, with the use of either (R)-2-methylpiperazine or (S)-2-methylpiperazine, resulting in noncentrosymmetric, polar, chiral structures that crystallize in the space group P21 (No. 4).
    No preview · Article · Aug 2013 · Crystal Growth & Design
  • Courtnay E. Shaner · Gregory M. Ferrence · T. Andrew Mitchell
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    ABSTRACT: Studies directed toward the isoindolinone core of muironolide A are described. An initial plan to implement an intramolecular Diels-Alder cycloaddition was thwarted by an undesired conjugate addition during the attempted preparation of the Diels-Alder substrate. A revised retrosynthetic analysis revealed a direct, albeit challenging, intermolecular Diels-Alder disconnection. Toward this end, a sterically hindered and electronically deactivated diene was utilized with N-phenylmaleimide to achieve a Diels-Alder cycloaddition.
    No preview · Article · Aug 2013 · Synlett
  • Timothy David Lash · Ashley M Toney · Kylie M Castans · Gregory M Ferrence
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    ABSTRACT: Benzitripyrranes were prepared by reacting diphenyl benzenedicarbinols with excess pyrrole in the presence of BF3.Et2O. These dipyrrolic compounds underwent acid catalyzed condensations with a pyrrole dialdehyde to afford good yields of diphenylbenziporphyrins, and further reaction with palladium(II) acetate gave stable organometallic derivatives. The X-ray crystal structure of a palladium(II) benziporphyrin showed that the system deviates significantly from planarity. Although the benzitripyrranes failed to give stable macrocyclic products with furan or thiophene dialdehydes, they afforded tetraphenyl heterobenziporphyrins upon reaction with diphenyl furan or thiophene dicarbinols and BF3.Et2O. Benziporphyrins and their heteroanalogues showed no indication of a diamagnetic ring current by proton NMR spectroscopy, but addition of TFA gave rise to the formation of weakly diatropic dications.
    No preview · Article · Aug 2013 · The Journal of Organic Chemistry
  • Ruoshi Li · Gregory M Ferrence · Timothy D Lash
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    ABSTRACT: MacDonald "2 + 2" condensation of a 1,2'-dipyrrylmethane dialdehyde with a 2,2'-dipyrrylmethane afforded a neo-confused porphyrin in 55% yield. In addition, a novel dihydroporphyrin with two appended pyrrolic units was isolated and structurally characterized.
    No preview · Article · Jul 2013 · Chemical Communications
  • Source
    Kara A Slater · Brad Andersh · Edward B Flint · Gregory M Ferrence
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    ABSTRACT: The title compound, CHO, is a phenyl-subsituted dihydro-pyran-dione in which the heterocycle adopts a boat conformation with the phenyl substituent canted 72.14 (5)° relative to the mean plane of the heterocycle.
    Full-text · Article · Jan 2013 · Acta Crystallographica Section E Structure Reports Online
  • Timothy D Lash · Komal Pokharel · Matthias Zeller · Gregory M Ferrence
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    ABSTRACT: The organometallic chemistry of azuliporphyrins has been extended to the first syntheses of rhodium(III) derivatives. Reaction of [Rh(CO)2Cl]2 with an azuliporphyrin in refluxing xylenes gave rhodium(III) azuliporphyrins in 62–67% yield. These derivatives incorporate solvent molecules as axial ligands and thereby introduce two carbon–rhodium bonds in a three-component reaction. The methylbenzyl ligands that are derived from xylenes overlie the π system of the porphyrinoid macrocycle, and proton NMR spectra show that these units are strongly shielded. The o-, m-, and p-xylene-derived complexes were characterized by X-ray crystallography, and this confirmed the presence of the central rhodium atom and the axial benzylic ligands. Additionally, when the azuliporphyrin was reacted with [Rh(CO)2Cl]2 in refluxing acetonitrile and then treated with acetone and basic alumina, a rhodium(III) azuliporphyrin with an acetone-derived axial ligand was generated. These results demonstrate that azuliporphyrins are superior organometallic ligands and therefore merit further investigation.
    No preview · Article · Oct 2012 · Chemical Communications

Publication Stats

1k Citations
370.14 Total Impact Points

Institutions

  • 2001-2015
    • Illinois State University
      • Department of Chemistry
      Нормальная, Illinois, United States
  • 2007
    • Salisbury University
      • Department of Chemistry
      Maryland, United States
  • 1999-2002
    • University of Alberta
      • Department of Chemistry
      Edmonton, Alberta, Canada
  • 1996-1998
    • Purdue University
      • Department of Chemistry
      ウェストラファイエット, Indiana, United States