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James T. Goettel Dr. Kazuhiko Matsumoto Dr. Hélène P. A. Mercier Prof. Gary J. Schrobilgen 《Angewandte Chemie (International ed. in English)》2016,55(44):13780-13783
The potent oxidizer and highly shock‐sensitive binary noble‐gas oxide XeO3 interacts with CH3CN and CH3CH2CN to form O3XeNCCH3, O3Xe(NCCH3)2, O3XeNCCH2CH3, and O3Xe(NCCH2CH3)2. Their low‐temperature single‐crystal X‐ray structures show that the xenon atoms are consistently coordinated to three donor atoms, which results in pseudo‐octahedral environments around the xenon atoms. The adduct series provides the first examples of a neutral xenon oxide bound to nitrogen bases. Raman frequency shifts and Xe?N bond lengths are consistent with complex formation. Energy‐minimized gas‐phase geometries and vibrational frequencies were obtained for the model compounds O3Xe(NCCH3)n (n=1–3) and O3Xe(NCCH3)n?[O3Xe(NCCH3)2]2 (n=1, 2). Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses were carried out to further probe the nature of the bonding in these adducts. 相似文献
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Dr. James T. Goettel Mark R. Bortolus Daniel G. Stuart Dr. Hélène P. A. Mercier Prof. Gary J. Schrobilgen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(69):15815-15829
Molten mixtures of XeF6 and CrVIOF4 react by means of F2 elimination to form [XeF5][Xe2F11][CrVOF5] ⋅ 2 CrVIOF4, [XeF5]2[CrIVF6] ⋅ 2 CrVIOF4, [Xe2F11]2[CrIVF6], and [XeF5]2[CrV2O2F8], whereas their reactions in anhydrous hydrogen fluoride (aHF) and CFCl3/aHF yield [XeF5]2[CrV2O2F8] ⋅ 2 HF and [XeF5]2[CrV2O2F8] ⋅ 2 XeOF4. Other than [Xe2F11][MVIOF5] and [XeF5][MVI2O2F9] (M=Mo or W), these salts are the only Group 6 oxyfluoro-anions known to stabilize noble-gas cations. Their reaction pathways involve redox transformations that give [XeF5]+ and/or [Xe2F11]+ salts of the known [CrVOF5]2− and [CrIVF6]2− anions, and the novel [CrV2O2F8]2− anion. A low-temperature Raman spectroscopic study of an equimolar mixture of solid XeF6 and CrOF4 revealed that [Xe2F11][CrVIOF5] is formed as a reaction intermediate. The salts were structurally characterized by LT single-crystal X-ray diffraction and LT Raman spectroscopy, and provide the first structural characterizations of the [CrVOF5]2− and [CrV2O2F8]2− anions, where [CrV2O2F8]2− represents a new structural motif among the known oxyfluoro-anions of Group 6. The X-ray structures show that [XeF5]+ and [Xe2F11]+ form ion pairs with their respective anions by means of Xe- - -F–Cr bridges. Quantum-chemical calculations were carried out to obtain the energy-minimized, gas-phase geometries and the vibrational frequencies of the anions and their ion pairs and to aid in the assignments of their Raman spectra. 相似文献
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Mark R. Bortolus Dr. Hélène P. A. Mercier Prof. Gary J. Schrobilgen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8935-8950
The reactions of the fluoride-ion donor, XeF6, with the fluoride-ion acceptors, M′OF4 (M′=Cr, Mo, W), yield [XeF5]+ and [Xe2F11]+ salts of [M′OF5]− and [M2O2F9]− (M=Mo, W). Xenon hexafluoride and MOF4 react in anhydrous hydrogen fluoride (aHF) to give equilibrium mixtures of [Xe2F11]+, [XeF5]+, [(HF)nF]−, [MOF5]−, and [M2O2F9]− from which the title salts were crystallized. The [XeF5][CrOF5] and [Xe2F11][CrOF5] salts could not be formed from mixtures of CrOF4 and XeF6 in aHF at low temperature (LT) owing to the low fluoride-ion affinity of CrOF4, but yielded [XeF5][HF2]⋅CrOF4 instead. In contrast, MoOF4 and WOF4 are sufficiently Lewis acidic to abstract F− ion from [(HF)nF]− in aHF to give the [MOF5]− and [M2O2F9]− salts of [XeF5]+ and [Xe2F11]+. To circumvent [(HF)nF]− formation, [Xe2F11][CrOF5] was synthesized at LT in CF2ClCF2Cl solvent. The salts were characterized by LT Raman spectroscopy and LT single-crystal X-ray diffraction, which provided the first X-ray crystal structure of the [CrOF5]− anion and high-precision geometric parameters for [MOF5]− and [M2O2F9]−. Hydrolysis of [Xe2F11][WOF5] by water contaminant in HF solvent yielded [XeF5][WOF5]⋅XeOF4. Quantum-chemical calculations were carried out for M′OF4, [M′OF5]−, [M′2O2F9]−, {[Xe2F11][CrOF5]}2, [Xe2F11][MOF5], and {[XeF5][M2O2F9]}2 to obtain their gas-phase geometries and vibrational frequencies to aid in their vibrational mode assignments and to assess chemical bonding. 相似文献
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Dr. Hélène P. A. Mercier Ulf Breddemann Dr. David S. Brock Mark R. Bortolus Prof. Gary J. Schrobilgen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(52):12105-12119
The noble-gas difluoride adducts, NgF2 ⋅ CrOF4 and NgF2 ⋅ 2CrOF4 (Ng=Kr and Xe), have been synthesized and structurally characterized at low temperatures by Raman spectroscopy and single-crystal X-ray diffraction. The low fluoride ion affinity of CrOF4 renders it incapable of inducing fluoride ion transfer from NgF2 (Ng=Kr and Xe) to form ion-paired salts of the [NgF]+ cations having either the [CrOF5]− or [Cr2O2F9]− anions. The crystal structures show the NgF2 ⋅ CrOF4 adducts are comprised of Ft−Ng−Fb- - -Cr(O)F4 structural units in which NgF2 is weakly coordinated to CrOF4 by means of a fluorine bridge, Fb, in which Ng−Fb is elongated relative to the terminal Ng−Ft bond. In contrast with XeF2 ⋅ 2MOF4 (M=Mo or W) and KrF2 ⋅ 2MoOF4, in which the Lewis acidic, F4(O)M- - -Fb- - -M(O)F3 moiety coordinates to Ng through a single M- - -Fb−Ng bridge, both fluorine ligands of NgF2 coordinate to CrOF4 molecules to form F4(O)Cr- - -Fb−Ng−Fb- - -Cr(O)F4 adducts in which both Ng−Fb bonds are only marginally elongated relative to the Ng−F bonds of free NgF2. Quantum-chemical calculations show that the Cr−Fb bonds of NgF2 ⋅ CrOF4 and NgF2 ⋅ 2CrOF4 are predominantly electrostatic with a small degree of covalent character that accounts for their nonlinear Cr- - -Fb−Ng bridge angles and staggered O−Cr- - -Fb−Ng−Ft dihedral angles. The crystal structures and Raman spectra of two CrOF4 polymorphs have also been obtained. Both are comprised of fluorine-bridged chains that are cis- and trans-fluorine-bridged with respect to oxygen. 相似文献
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Mark R. Bortolus Dr. Hélène P. A. Mercier Dr. David S. Brock Prof. Gary J. Schrobilgen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(15):e202103729
The NgF2 ⋅ MOF4 (Ng=Kr, Xe; M=Mo, W) and XeF2 ⋅ 2MOF4 complexes were synthesized in anhydrous HF (aHF) solvent and melts, respectively. Their single-crystal X-ray diffraction (SCXRD) structures show NgF2 ⋅ MOF4 and XeF2 ⋅ 2MOF4 have Ft−Ng−Fb- - -M arrangements, in which the NgF2 ligands coordinate to MOF4 through Ng−Fb- - -M bridges. The XeF2 ligands of XeF2 ⋅ 2MOF4 also coordinate to F3OM−Fb’- - -M'OF4 moieties through Xe−Fb- - -M bridges to form Ft−Xe−Fb- - -M(OF3)−Fb’- - -M'OF4, where XeF2 coordinates trans to the M=O bond and Fb’ coordinates trans to the M’=O bond. The Ng−Ft, Ng−Fb, and M- - -Fb bond lengths of NgF2 ⋅ nMOF4 are consistent with MOF4 and F3OM−Fb’- - -M'OF4 fluoride-ion affinity trends: CrOF4<MoOF4<WOF4≈F3OMo−Fb’- - -Mo'OF4<F3OW−Fb’- - -W'OF4. The [- -(F4OMo)(μ3-F)H- - -(μ-F)H- -]∞ solvate was also synthesized in aHF and characterized by SCXRD. Quantum-chemical calculations show the M- - -Fb bonds of NgF2 ⋅ MOF4 and XeF2 ⋅ 2MOF4 are predominantly electrostatic, σ-hole type bonds. 相似文献
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两种镍的配合物[Ni(NH2CH2CH2CH2NH2)3]Cl2 (1)和[Ni(C6H4N2H4)2Cl2] (2)已经被合成并且通过红外和单晶X射线衍射分析对其进行了表征。在配合物1中,镍原子处于手性假八面体[NiN6]的几何构型中,它与三个1,3-丙二胺分子形成了三个六元环。在配合物2中,镍原子除了与两个o-苯二胺分子通过四个Ni-N键形成两个五元环外,它还与两个Cl原子配位形成了反式Ni-Cl2,这不同于以往报道过的镍的二胺配合物。这两个镍的配合物被MAO, MMAO或Et2AlCl活化后,对乙烯的二聚合或三聚合显示了很好的催化活性[对于配合物2,催化活性达到3.59×106 g mol-1 (Ni) h-1]。 相似文献
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Xenon(II) Polyfluoridotitanates(IV): Synthesis and Structural Characterization of [Xe2F3]+ and [XeF]+ Salts
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Kristian Radan Dr. Evgeny Goreshnik Prof. Boris Žemva 《Angewandte Chemie (International ed. in English)》2014,53(50):13715-13719
Thermal reaction between XeF2 and excess TiF4 resulted in the unexpected formation of a highly ionized XeII species. The products [Xe2F3][Ti8F33] and [XeF]2[Ti9F38] represent the first examples of [Xe2F3]+ and [XeF]+ compounds, which differ from known XeII salts containing discrete fluoride anions with pentavalent metalloid/metal centers. A new structural type of 2D polyanion [Ti8F33]? and the formation and structure of the novel 1D [Ti9F38]2? are discussed. Both products were characterized by single‐crystal X‐ray analysis and Raman spectroscopy. 相似文献
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Andreas Reisinger Dr. Nils Trapp Dr. Carsten Knapp Dr. Daniel Himmel Dr. Frank Breher Prof. Heinz Rüegger Dr. Ingo Krossing Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(37):9505-9520
Compounds including the free or coordinated gas‐phase cations [Ag(η2‐C2H4)n]+ (n=1–3) were stabilized with very weakly coordinating anions [A]? (A=Al{OC(CH3)(CF3)2}4, n=1 ( 1 ); Al{OC(H)(CF3)2}4, n=2 ( 3 ); Al{OC(CF3)3}4, n=3 ( 5 ); {(F3C)3CO}3Al‐F‐Al{OC(CF3)3}3, n=3 ( 6 )). They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of ethene in CH2Cl2 solution. As a reference we also prepared the isobutene complex [(Me2C?CH2)Ag(Al{OC(CH3)(CF3)2}4)] ( 2 ). The compounds were characterized by multinuclear solution‐NMR, solid‐state MAS‐NMR, IR and Raman spectroscopy as well as by their single crystal X‐ray structures. MAS‐NMR spectroscopy shows that the [Ag(η2‐C2H4)3]+ cation in its [Al{OC(CF3)3}4]? salt exhibits time‐averaged D3h‐symmetry and freely rotates around its principal z‐axis in the solid state. All routine X‐ray structures (2θmax.<55°) converged within the 3σ limit at C?C double bond lengths that were shorter or similar to that of free ethene. In contrast, the respective Raman active C?C stretching modes indicated red‐shifts of 38 to 45 cm?1, suggesting a slight C?C bond elongation. This mismatch is owed to residual librational motion at 100 K, the temperature of the data collection, as well as the lack of high angular data owing to the anisotropic electron distribution in the ethene molecule. Therefore, a method for the extraction of the C?C distance in [M(C2H4)] complexes from experimental Raman data was developed and meaningful C?C distances were obtained. These spectroscopic C?C distances compare well to newly collected X‐ray data obtained at high resolution (2θmax.=100°) and low temperature (100 K). To complement the experimental data as well as to obtain further insight into bond formation, the complexes with up to three ligands were studied theoretically. The calculations were performed with DFT (BP86/TZVPP, PBE0/TZVPP), MP2/TZVPP and partly CCSD(T)/AUG‐cc‐pVTZ methods. In most cases several isomers were considered. Additionally, [M(C2H4)3] (M=Cu+, Ag+, Au+, Ni0, Pd0, Pt0, Na+) were investigated with AIM theory to substantiate the preference for a planar conformation and to estimate the importance of σ donation and π back donation. Comparing the group 10 and 11 analogues, we find that the lack of π back bonding in the group 11 cations is almost compensated by increased σ donation. 相似文献
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Syntheses and Crystal Structures of Copper and Silver Complexes with the Ylide Ph3PCHP(O)PPh2 as Ligand
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The reactivity of the hydrolysis product of hexaphenylcarbodiphosphorane, PPh3CHP(O)Ph2, towards different soft Lewis acids, such as CuI and Ag[BF4] are reported. While CuI exclusively binds at the ylidic carbon atom, reaction of the silver cation in CH2Cl2 leads to proton abstraction from the solvent to give the cation [PPh3CH2P(O)Ph2]+. Surprisingly, Ag+ replaces the methyl group of [PPh3CHMeP(O)Ph2]+ to produce a dimeric complex, in which Ag+ is coordinated to C and O forming an eight membered ring. The compounds were characterized by spectroscopic methods and X‐ray diffraction. 相似文献
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Arylation of TeCl4 with arylboroxine–pyridine complexes [(RBO)3·C5H5N, where R = m‐O2NC6H4 ( 1 ), p‐O2NC6H4 ( 2 ), m‐NCC6H4 ( 3 ), p‐NCC6H4 ( 4 )] and advantageous moisture provided good yields of the pyridinium aryltetrachlorotellurates [C5H6N][RTeCl4] [R = m‐O2NC6H4 ( 5 ), p‐O2NC6H4 ( 6 ), m‐NCC6H4 ( 7 ), p‐NCC6H4 ( 8 )]. Compounds 5 and 8 have been investigated by X‐ray crystallography. Key features of both crystal structures are intermolecular secondary Te???Cl interactions between the aryltetrachlorotellurate anions and weak association of the cations and anions. Electrospray mass spectra of compound 5 reveal that the associative interactions also play a role in solution. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
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Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)] · 7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)] · 4H2O (NDUS1), and one uranyl selenate‐selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets. 相似文献
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Two copper(I) complexes of compositions [Cu(HL)I]2 · EtOH ( 1 ) and [Cu(HL)3]I · MeOH ( 2 ) were synthesized via the reactions of HL [HL = 2(4,5‐diphenyl‐1H‐imidazol‐2‐yl)pyridine] and CuI in EtOH and MeOH, respectively, under solvothermal conditions. The complexes were characterized by X‐ray single crystal diffraction, IR spectroscopy, and elemental analysis. Compounds 1 and 2 are catalytically active towards ketalization reaction, giving various ketals under mild conditions. 相似文献