A5081153980- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Crystallography and molecular interactions
- Organometallic Complex Synthesis and Catalysis
- Metal complexes synthesis and properties
- Synthesis and characterization of novel inorganic/organometallic compounds
- Metal-Catalyzed Oxygenation Mechanisms
- Coordination Chemistry and Organometallics
- Radioactive element chemistry and processing
- Organometallic Compounds Synthesis and Characterization
- Lanthanide and Transition Metal Complexes
- Organoboron and organosilicon chemistry
- Magnetism in coordination complexes
- Asymmetric Hydrogenation and Catalysis
- Crystal structures of chemical compounds
- Oxidative Organic Chemistry Reactions
- Nuclear Materials and Properties
- Chemical Synthesis and Characterization
- Inorganic Chemistry and Materials
- Silicone and Siloxane Chemistry
- Radical Photochemical Reactions
- Nuclear reactor physics and engineering
- Neural Networks and Applications
- Ferrocene Chemistry and Applications
- Catalytic C–H Functionalization Methods
Helmholtz-Zentrum Dresden-Rossendorf
2021-2025
Trinity College Dublin
2019-2024
RMIT University
2015-2023
TU Bergakademie Freiberg
2009-2021
Technische Universität Braunschweig
2021
University of Konstanz
2021
University of Münster
2021
Technical University of Munich
2021
Clausthal University of Technology
2021
Walter de Gruyter (Germany)
2021
Aromatic π-stacking is a weakly attractive, noncovalent interaction often found in biological macromolecules and synthetic supramolecular chemistry. The weak nondirectional nature of can present challenges the design materials owing to their weak, nature. However, when aromatic π-systems contain an unpaired electron, stronger attraction involving face-to-face π-orbital overlap possible, resulting covalent so-called "pancake" bonds. Two-electron, multicenter single pancake bonds are well...
Abstract Cr-doped UO 2 is a leading accident tolerant nuclear fuel where the complexity of Cr chemical states in bulk material has prevented acquisition an unequivocal understanding redox chemistry and mechanism for incorporation matrix. To resolve this, we have used electron paramagnetic resonance, high energy resolution fluorescence detection X-ray absorption near structure extended fine spectroscopic measurements to examine single crystal grains material. Ambient condition grains, which...
[FeII(NCCH3)(NTB)](OTf)2 (NTB = tris(2-benzimidazoylmethyl)amine, OTf trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ3-iodane (PhIF2) in the presence of a variety saturated hydrocarbons, resulting oxidative fluorination hydrocarbons moderate-to-good yields. Kinetic and product analysis point towards hydrogen atom transfer oxidation prior to fluorine radical rebound form fluorinated product. The combined evidence supports formation formally FeIV(F)2 oxidant that performs...
In their + V and VI oxidation states, actinide elements (U, Np, Pu) are commonly encountered in characteristic linear dioxo structures, known as actinyl ions (AnO2n+; An = U, Pu, n 1, 2). A systematic understanding of the structural redox behavior AnVO2+/AnVIO22+ complexes is expected to provide valuable information for controlling natural environments nuclear fuel cycles while enabling development spintronics new reactivities that utilize anisotropic spin 5f electrons. However, trends...
Heteroleptic AnIV (An = U, Np) chlorido-ketoenaminate complexes of the type [AnCl2(TFB-tBuA)2(THF)] (An-1 type: U-1, Np-1; TFB-tBuA 4-(tert-butylamino)-1,1,1-trifluorobut-3-en-2-one) and homoleptic NpIV heteroarylalkenolate [Np(PyTFP)4] (Np-2, PyTFP 1-(pyridin-2-yl)-3,3,3-trifluoroprop-1-en-2-ol) [Np(DMOTFP)4] (Np-3, DMOTFP 1-(4,5-dimethyloxazol-2-yl)-3,3,3-trifluoroprop-1-en-2-ol) were synthesized characterized (SC-XRD, NMR, Vis-NIR, MS). While their solid-state structures compare well to...
Oxygenases have been postulated to utilize d4 FeIV and d8 CuIII oxidants in proton-coupled electron transfer (PCET) hydrocarbon oxidation. In order explore the influence metal ion d-electron count can hold over PCET reactivity, two metastable high-valent metal-oxygen adducts, [NiIII(OAc)(L)] (1b) [CuIII(OAc)(L)] (2b), L = N,N'-(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamidate, were prepared from their low-valent precursors [NiII(OAc)(L)]- (1a) [CuII(OAc)(L)]- (2a). The complexes 1a/b-2a/b...
The group 14 element's ligand role in N,S-bridged transition metal complexes was shown to depend on both atoms’ substitution patterns.
We anticipate high-valent metal-fluoride species will be highly effective hydrogen atom transfer (HAT) oxidants because of the magnitude H-F bond (in product) that drives HAT oxidation. prepared a dimeric Fe
Nitrilotris(methylenephenylphosphinic) acid (NTPAH3) was silylated using hexamethyldisilazane to produce the tris(trimethylsilyl) derivative NTPA(SiMe3)3. From latter, upon alcoholysis in chloroform, NTPAH3 could be recovered. Thus, a new modification of that phosphinic formed. Meanwhile, synthesized aqueous hydrochloric crystallized space group P3c1 with formation O-H⋅⋅⋅O H-bonded networks (NTPAH3P), chloroform crystals R3c formed (NTPAH3M), constituents which are individual molecules...
Complexes of Sn(II), Sn(IV), Ge(IV), and Si(IV) with the ambidentate pyridine-2-thiolato ligand (PyS-) were synthesized characterized by multinuclear NMR spectroscopy single-crystal X-ray diffractometry. Comparison structures E(PyS)2Cl2 (E=Sn, Ge, Si) E(PyS)4 allows for insights into group 14 coordination chemistry this chelator in dependence thiophilicity central atom corresponding complex. Furthermore, crystal structure Sn(PyS)2 reveals two different modes its constituents, i.e., packing...
Metal-halides that perform proton coupled electron-transfer (PCET) oxidation are an important new class of high-valent oxidant. In investigating metal-dihalides, we reacted [FeIII(Cl)(T(OMe)PP)] (1, T(OMe)PP = meso-tetra(4-methoxyphenyl)porphyrinyl) with (dichloroiodo)benzene. An FeIII-meso-chloro-isoporphyrin complex [FeIII(Cl)2(T(OMe)PP-Cl)] (2) was obtained. 2 characterized by electronic absorption, 1H NMR, EPR, and X-ray absorption spectroscopies mass spectrometry support from...
Isostructural trivalent lanthanide and actinide amidinates bearing the N,N'-bis(isopropyl)benzamidinate (iPr2BA) ligand [LnIII/AnIII(iPr2BA)3] (Ln = La, Nd, Sm, Eu, Yb, Lu; An U, Np) have been synthesized characterized in both solid solution states. All compounds were examined state utilizing single crystal X-ray diffraction (SC-XRD), revealing a notable deviation series with shortened bond lengths compared to trend series, suggesting nonionic contribution actinide–ligand bonding....
Reactions of tin(IV) complexes the type Sn(PyS)2X2 (X = Cl, PyS, Ph; PyS pyridine-2-thiolate) with Pd(PPh3)4 provide easy access to novel heterometallic Pd–Sn bonds. Electronic characteristics this connection were analysed by X-ray crystallography, 119Sn Mössbauer spectroscopy and quantum chemical analyses.
Proceeding our initial studies of compounds with formally dative TM→Si bonds (TM = Ni, Pd, Pt), which feature a paddlewheel arrangement four (N,S) or (N,N) bridging ligands around the TM–Si axis, current study shows that (N,O)-bidentate ligand 2-pyridyloxy (pyO) is also capable systems (shown for TM Cu). Reactions MeSi(pyO)3 [PdCl2(NCMe)2] and CuCl afforded MeSi(µ-pyO)4PdCl (1) MeSi(µ-pyO)3CuCl (2), respectively. In latter case, some crystals Cu(II) compound MeSi(µ-pyO)4CuCl (3) were...
Neutral bi-, tri-, and tetradentate ligands of the type Ph3-xSb(L)x [x = 1 (1), 2 (2), 3 (3). L La phthalimidinyl (1a, 2a, 3a), Lb 2-pyridyloxy (1b, 2b, 3b)] have been synthesized characterized. Reaction Sb,E Sb,E2 with [RuCl2(PPh3)3] proceeded under anion scrambling formation complexes [Ph2Sb(μ-L)2Ru(PPh3)(μ-Cl)]2 (5) or [PhSb(μ-L)3RuCl(PPh3)] (8) in addition to various byproducts. Reactions Sb,E3 afforded highly diverse product mixtures. Deliberate syntheses types 5 8 were successful by...
In the course of our investigations coordination chemistry trivalent antimony (Sb) compounds, we studied heteronuclear complexes formed in reactions compounds RSb(pyS)2 (R = pyS, Ph; pyS– pyridine-2-thiolate) with [Pt(PPh3)4], i.e., [(R)Sb(μ-pyS)2Pt(PPh3)] 1; R Ph, 2). The reaction 1 o-chloranil proceeds cleanly elimination 2,2′-dipyridyl disulfide and formation salt [(PPh3)Pt(μ-pyS)2Sb(μ-pyS)2Pt(PPh3)]+[Sb(C6Cl4O2)2]− (3III), which features cation 3+. charge-neutral, unsymmetrically...
In exploring terminal nickel-oxo complexes, postulated to be the active oxidant in natural and non-natural oxidation reactions, we report synthesis of pseudo-trigonal bipyramidal NiII complexes (K)[NiII (LPh )(DMF)] (1[DMF]) (NMe4 )2 [NiII )(OAc)] (1[OAc]) =2,2',2''-nitrilo-tris-(N-phenylacetamide); DMF=N,N-dimethylformamide; - OAc=acetate). Both were characterized using NMR, FTIR, ESI-MS, X-ray crystallography, showing LPh ligand bind a tetradentate fashion, together with an ancillary...
Although silacyclobutanes appear susceptible to penta- and hexacoordination of their Si atoms because inherent so-called ring-strain-release Lewis acidity, we succeeded in synthesizing a pentacoordinate (trigonal-bipyramidal) silacyclobutane with equatorial Si−C bonds. A related an axial−equatorial situation was found by quantum-chemical calculations have low energy barrier (ca. 3 kcal/mol) for its transformation into isomer exclusively
High-valent metal-halides have come to prominence as highly effective oxidants. A direct comparison of their efficacy against that traditional metal-oxygen adducts is needed. [AuIII(Cl)(terpy)](ClO4)2 (1; terpy = 2,2':6',2-terpyridine) readily oxidized substrates bearing O-H and C-H bonds via a hydrogen atom transfer mechanism. with [AuIII(OH)(terpy)](ClO4)2 (2) showed 1 was kinetically superior oxidant respect 2 for all tested. We ascribe this the greater thermodynamic driving force imbued...
The tin(IV) compounds MexSn(2-C6F4PPh2)4-x (1, x = 1; 2, 2) and ClSn(2-C6F4PPh2)3 (3) were obtained from the reactions of 2-LiC6F4PPh2 with MeSnCl3 (3:1), Me2SnCl2 (2:1), or SnCl4 respectively. in different stoichiometric ratios (4:1-1:1) gave 3 as main product. Compound Cl2Sn(2-C6F4PPh2)2 (4) was formed transmetalation reaction [AuCl(tht)] but could not be isolated. 1 2 react palladium(0) sources {[Pd(PPh3)4] [Pd(allyl)Cp]} by oxidative addition one their Sn-CAryl bonds to formation...
Abstract The monazite-cheralite solid solutions Ln PO 4 -Ca 0.5 Th with = La, Gd were prepared via a co-precipitation route, showcasing an optimised, scalable synthesis procedure for possible waste form accommodating high level liquid streams. A distortion of the cheralite structure respect to monazite was observed throughout both as evidenced by deviation lattice parameters from linear behaviour known other solutions. Using temperature flux method, single crystals grown first time in-depth...
Here, we report the synthesis of 6-(6-methyl-1,2,4,5-tetrazine-3-yl)-2,2′-bipyridine (MTB) ligand that has been developed for lanthanide/actinide separation. A multimethod study complexation MTB with trivalent actinide and lanthanide ions is presented. Single-crystal X-ray diffraction measurements reveal formation [Ce(MTB)2(NO3)3], [Pr(MTB)(NO3)3H2O], [Ln(MTB)(NO3)3MeCN] (Ln = Nd, Sm, Eu, Gd). In addition, Cm(III) in solution was studied by time-resolved laser fluorescence spectroscopy. The...