A5076108048- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organometallic Complex Synthesis and Catalysis
- Magnetism in coordination complexes
- Crystallography and molecular interactions
- Metal-Catalyzed Oxygenation Mechanisms
- Metal complexes synthesis and properties
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Lanthanide and Transition Metal Complexes
- Electrocatalysts for Energy Conversion
- Porphyrin and Phthalocyanine Chemistry
- Asymmetric Hydrogenation and Catalysis
- Synthesis and Catalytic Reactions
- Synthetic Organic Chemistry Methods
- Catalytic C–H Functionalization Methods
- Molecular Sensors and Ion Detection
- Luminescence and Fluorescent Materials
- Metalloenzymes and iron-sulfur proteins
- Carbon dioxide utilization in catalysis
- Advanced battery technologies research
- CO2 Reduction Techniques and Catalysts
- Organoboron and organosilicon chemistry
- Analytical Chemistry and Sensors
- Advanced MRI Techniques and Applications
- MRI in cancer diagnosis
National Central University
2024-2025
Loyola University Chicago
2016-2023
Indiana University Bloomington
2014-2022
New Mexico State University
2013-2017
University of Iowa
2008-2009
Kaohsiung Medical University
2006
Abstract The catalytic reactivity of the high‐spin Mn II pyridinophane complexes [(Py 2 NR )Mn(H O) ] 2+ (R=H, Me, t Bu) toward O formation is reported. With small macrocycle N‐substituents Me), catalytically disproportionate H in aqueous solution; with a bulky substituent (R= Bu), this reaction shut down, but complex becomes active for electrocatalytic oxidation. Control experiments are support homogeneous molecular catalyst and preliminary mechanistic studies suggest that mononuclear. This...
Abstract Thermolysis of the iron(IV) nitride complex [PhB( t BuIm) 3 FeN] with styrene leads to formation high‐spin iron(II) aziridino Fe‐N(CH 2 CHPh)]. Similar aziridination occurs both electron‐rich and electron‐poor styrenes, while bulky styrenes hinder reaction. The CHPh)] acts as a synthon, reacting generate their corresponding complexes, that is, aziridine cross‐metathesis. Reaction Me SiCl releases N‐functionalized SiN(CH CHPh) simultaneously generating FeCl]. This closes synthetic...
The iron(IV) nitrido complex PhB(MesIm)3Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide PhB(MesIm)3Fe(η5-C4H4N) in high yield. mechanism of product formation is proposed involve sequential [4 + 1] cycloaddition and retro Diels–Alder reactions. Surprisingly, reaction 1,4-cyclohexadiene yields same iron-containing product, albeit substantially lower mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from provide cyclohexadienyl...
High-oxidation-state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect apical ligand on spin-state preferences threefold symmetric iron(IV) tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(ImR)3}FeN], R tBu (1), Mes (mesityl, 2) related triplet 1) imido complexes, [{PhB(ImR)3}Fe(NR′)]+, Mes, R′...
The new iron(IV) nitride complex PhB(iPr2Im)3Fe≡N reacts with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB(iPr2Im)3Fe(CN)(N2)(BAC). This unusual example a four-electron reaction involves carbon atom transfer from BAC create cyanide ligand along the alkyne iPr2N-C≡C-NiPr2. iron is in equilibrium an N2-free species. Further CO leads formation analogue, which can be independently prepared using NaCN as source, while B(C6F5)3 provides cyanoborane derivative.
A tripodal ligand constructed solely from mesoionic carbene donors is reported. The donor strength of this lower than most imidazol-2-ylidene-based tris(carbene)borate ligands, as measured by IR spectroscopy {NiNO}10 and {Mn(CO)3}+ derivatives. attenuated proposed to be due the collective electron-withdrawing effect ligand's aryl substituents.
The bulky bis(carbene)borate ligand Ph2B(tBuIm)2– stabilizes low-coordinate and low-valent iron complexes. four-coordinate iron(II) complex Ph2B(tBuIm)2FeCl(THF) is a precursor to the low-spin iron(I) Ph2B(tBuIm)2Fe(CO)3. Despite reversible reduction wave in cyclic voltammogram, access iron(0) [Ph2B(tBuIm)2Fe(CO)3]− requires under CO atmosphere. Without excess CO, KC8 leads formation of dimer K2[Ph2B(tBuIm)2Fe(CO)2] along with loss CO. Each center this adopts distorted-square-planar...
A series of four- and five-coordinate Ni(II) complexes Cz tBu(Pyr iPr)2NiX (1-3 1·THF-3·THF), where X = Cl, Br, I, were synthesized fully characterized by NMR UV-vis spectroscopy, X-ray crystallography, cyclic voltammetry, density functional theory calculations. The solid-state structures 1-3 reveal rare examples seesaw complexes. In solution, bind reversibly to a THF molecule form adducts. electronic transitions in the visible region (630-680 nm), attributed LMCT bands, for 1 → 3 exhibit...
A new design of a low-coordinate iron complex, bearing hemilabile ligand, served as an effective hydrosilylation pre-catalyst.
Irradiation of a disphenoidal Ni(II) azido complex, [Cz tBu(Pyr iPr)2NiN3] (1), revealed an unprecedented nickel iPr)(NH2-Pyr iPr)] (2), in >90% isolated yield. As evidenced by single-crystal X-ray diffraction, 2 is produced double intramolecular C-H activation putative nickel-nitridyl intermediate, iPr)2Ni-⃛N•]. Calculations support the generation intermediate with significant nitridyl radical character after loss N2, which, turn, undergoes tandem activations, leading to functionalized...
Electron-rich tris(guanidinato) complexes of Ir(III), [Ir{ArNC(NR(2))NAr}(3)] (where R = Me or Et; Ar Ph 4-MeC(6)H(4)), were synthesized from the respective [Ir{ArNC(NR(2))NAr}(C(8)H(14))(2)] precursors (C(8)H(14) cis-cyclooctene), are air-sensitive, and can be electrochemically oxidized in two one-electron transfer steps. The first electron is reversible occurs at much lower potentials than typical for Ir(III). Chemical oxidation by [FeCp(2)]PF(6) afforded isolable, paramagnetic Ir(IV)...
Abstract The pyridinophane complex [Mn(Py 2 N )(H O) ] 2+ catalyses the disproportionation of H O in aqueous solution over a wide pH range. Kinetic investigations reveal an induction period, which is proposed to involve formation hydroperoxo intermediate, as well evidence for catalyst self‐inhibition. A catalytic cycle involving mononuclear intermediates has been proposed. Spectroscopic under turnover conditions are consistent with this proposal and show that resting state Mn II complex....
Abstract The catalytic reactivity of the high‐spin Mn II pyridinophane complexes [(Py 2 NR )Mn(H O) ] 2+ (R=H, Me, t Bu) toward O formation is reported. With small macrocycle N‐substituents Me), catalytically disproportionate H in aqueous solution; with a bulky substituent (R= Bu), this reaction shut down, but complex becomes active for electrocatalytic oxidation. Control experiments are support homogeneous molecular catalyst and preliminary mechanistic studies suggest that mononuclear. This...
The bulky bis(carbene)borate ligand H2B(tBuIm)2– allows for the synthesis of three- and four-coordinate iron(II) complexes, including heteroleptic H2B(tBuIm)2FeN(TMS)2 homoleptic [H2B(tBuIm)2]2Fe. magnetic properties these coordinatively unsaturated complexes have been characterized by SQUID magnetometry, but no evidence single-molecule magnet behavior is observed, despite large negative uniaxial zero field splitting. three-coordinate complex serves as a precursor mixed carbene...
Abstract Thermolysis of the iron(IV) nitride complex [PhB( t BuIm) 3 FeN] with styrene leads to formation high‐spin iron(II) aziridino Fe‐N(CH 2 CHPh)]. Similar aziridination occurs both electron‐rich and electron‐poor styrenes, while bulky styrenes hinder reaction. The CHPh)] acts as a synthon, reacting generate their corresponding complexes, that is, aziridine cross‐metathesis. Reaction Me SiCl releases N‐functionalized SiN(CH CHPh) simultaneously generating FeCl]. This closes synthetic...
Benzo-fused dipyrrins are π-extended analogs of conventional dipyrrins, which exhibit bathochromically shifted absorption and possess the synthetic capability to bind various metal ions. We aimed investigate potential benzo-fused in complexation with transition metals. Two new complexes Pd2+ Pt2+ were synthesized characterized. X-ray crystallography reveals that both a zigzag geometry square planar coordination central metal. The complex possesses very weak fluorescence at 665 nm, while is...
Mononuclear [Ir{ArNC(NR(2))NAr}(C(8)H(12))] complexes (where R = Me or Et; Ar Ph, 4-MeC(6)H(4), 2,6-Me(2)C(6)H(3); and C(8)H(12) 1,5-cyclooctadiene) were synthesized from the neutral N,N-dialkyl-N',N''-diarylguanidines via deprotonation transmetalation. As confirmed by single-crystal structure determinations, guanidinato(1-) ligands coordinate low-valent d(8) Ir(I) center in an N,N'-chelating binding mode, (13)C NMR chemical shifts of alkene carbon atoms establish that these function as...
Electronic structure calculations are performed to characterise the structures, energies, and spectroscopic data for a series of four-coordinate tris(carbene)borate {NiNO}10 complexes. There is excellent agreement between computational experimental results known complexes, allowing structure–function relationships be delineated. Calculations that provide insights into synthetic accessibility nickel(IV) nitrides by oxygen atom abstraction from these complexes also reported.
Synthesis and characterization of a rare nitrido-bridged vanadium(<sc>iv</sc>) dimer complex <italic>via</italic> both V<sup>III</sup>–N<sub>2</sub> V<sup>III</sup>–N<sub>3</sub> activation by chemical reduction.