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71.
Glen B. Deacon Alex Gitlits Gerd Zelesny Dirk Stellfeldt Gerd Meyer 《无机化学与普通化学杂志》1999,625(5):764-772
The complexes [K(H2O)2LnL2] (Ln = La or Nd; L = 1,2‐benzenedisulfonate) and [K(H2O)Yb(H2O)4L2] were initially isolated fortuitously from attempts to prepare the corresponding Ln2L3 complexes from Ln2O3 and H2L in water. Indeed the bulk products from these reactions have the composition Ln2L3. Subsequently, deliberate syntheses by reacting equimolar amounts of Ln2L3 with K2L in water gave the complexes in good yield. X‐ray crystal structures of [K(H2O)2LnL2] (Ln = La or Nd) showed the complexes to be isostructural with a two dimensional polymeric network structure in which LnL2 units are linked into chains crosslinked by potassium ions. Each Ln is nine coordinate with solely sulfonate oxygen donor atoms. Between adjacent lanthanoid ions there are three different types of sulfonate bridges and two examples of each. Most noteworthy is highly unsymmetrical bridging through μ‐η2‐sulfonate oxygen atoms. Consequently, one Ln–O bond is ca. 0.5 Å longer than the other eight. Potassium is nine‐coordinate with seven sulfonate oxygen atoms and two aqua ligands, and surprisingly <K–O(sulfonate)> is much longer than <K–O(H2O)>. Pairs of potassium ions are linked by two μ‐η2‐sulfonate oxygen atoms, which are unsymmetrically bridging. The structure of [K(H2O)Yb(H2O)4L2] comprises discrete tetranuclear units containing two independent ytterbium ions, each coordinated by four water molecules and two chelating (via seven membered rings) disulfonate ligands, and two potassium ions, each coordinated by six sulfonate oxygen atoms and a water molecule. For each potassium, four of the coordinated sulfonate oxygen atoms are from sulfonate ligands bonded to one ytterbium atom and two from sulfonate ligands attached to the other ytterbium atom. In contrast to the Nd and La complexes, <K–O(sulfonate)> is shorter than <K–O(H2O)>. 相似文献
72.
73.
Julia Rüger Christopher Timmermann Dr. Alexander Villinger Alexander Hinz Dr. Dirk Hollmann Prof. Dr. Wolfram W. Seidel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11191-11195
The capability of donor‐substituted alkynes to link different metal ions in a side‐on carbon donor‐chelate coordination mode is extended from the donor centers S and P to the second period element N. The complex [Tp′W(CO)2{η2‐C2(S)(NHBn)}] (Tp′=hydrido‐tris(3,5‐dimethylpyrazolyl)borate, Bn=benzyl) bearing a terminal sulfur atom and a secondary amine substituent is accessible by a metal‐template synthesis. Subsequent deprotonation allowed the formation of remarkably stable heterobimetallic complexes with the [(η5‐C5H5)Ru(PPh3)] and the [Ir(ppy)2] moiety. Electrochemical and spectroscopic investigations (cyclic voltammetry, IR, UV/Vis, luminescence, EPR), as well as DFT calculations, and X‐ray structure determinations of the W–Ru complex in two oxidation states reveal a strong metal–metal coupling but also a limited delocalization of excited states. 相似文献
74.
Dibutylmagnesium (contaminated with Al(n-Bu)3; nMg:nAl ca. 1:0.2) was found to react with MeOCH2CH2OH followed by the addition of PhSCH(Me)Ph in the presence of 0.2 equiv n-butyllithium yielding [Mg7(μ3-OCH2CH2OMe)6(μ-OCH2CH2OMe)6][Al(n-Bu)4]2 (1) as the principal product (yield 40–45% referred to MeOCH2CH2OH). The single-crystal X-ray diffraction analysis revealed that the centrosymmetric cationic heptamagnesium complex is built up from seven edge-shared MgO6 octahedra. The [Al(n-Bu)4]− anions adopt approximately a tetrahedral AlC4 symmetry. 1H, 13C and 27Al NMR spectroscopic measurements showed that in THF solution the structures both of the heptamagnesium complex and the tetrabutylaluminate anion are preserved and that there are no cation–anion interactions reducing the symmetry. The 27Al resonance (151.6 ppm) was found to be very sharp (w1/2 = 5 Hz), the coupling constant 1J(27Al,13C) amounts to 72.3 Hz. 相似文献
75.
Tastet L Schaumlöffel D Bouyssiere B Lobinski R 《Analytical and bioanalytical chemistry》2006,385(5):948-953
A method based on ICP collision-cell MS detection in capillary HPLC was developed to gain an insight into the purity and identity of selenium-containing proteins separated by 1-D and 2-D electrophoresis. The bands and spots obtained after the separation of water-soluble proteins in selenized yeast were digested with trypsin prior to chromatography. Selenium could be detected down to the subpicogram level. The method, assisted by information obtained by MALDI TOF MS on the 5000 Da cut-off fraction, permitted the purity of bands and spots to be estimated and the efficiency of tryptic digestion and the quantity of selenium present in individual peptides to be evaluated. Owing to the high sensitivity and the lack of matrix suppression effects, the method provided chromatograms with signal-to-noise ratios of 10–1000 in conditions where the common ES Q–TOF MS detection failed.
相似文献
76.
Guldi DM Rahman GM Qin S Tchoul M Ford WT Marcaccio M Paolucci D Paolucci F Campidelli S Prato M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(8):2152-2161
Dispersible single-walled carbon nanotubes grafted with poly(4-vinylpyridine), SWNT-PVP, were tested in coordination assays with zinc tetraphenylporphyrin (ZnP). Kinetic and spectroscopic evidence corroborates the successful formation of a SWNT-PVPZnP nanohybrid. Within this SWNT-PVPZnP nanohybrid, static electron-transfer quenching (2.0+/-0.1) x 10(9) s(-1) converts the photoexcited-ZnP chromophore into a radical-ion-pair state with a microsecond lifetime, namely one-electron oxidized-ZnP and reduced-SWNT. 相似文献
77.
The structure of proline in [proline + K]+ has been investigated in the gas phase using high level DFT and MP2 calculations and infrared photo dissociation spectroscopy with a free electron laser (FELIX). The respective FELIX spectrum of [proline + K]+ matches convincingly the calculated spectra of two structurally closely related and nearly iso-energetic zwitterionic salt bridge (SB) structures. An additional unresolved band at approximately 1725 cm(-1) matching with the characteristic CO stretching mode of charge solvation (CS) structures points toward the presence of a minor population of these conformers of proline in [proline + K]+. However, theory predicts a significant energy gap of 18.9 kJ mol(-1) (B3LYP/6-311++G(2d,2p)) or 15.6 kJ mol(-1) (MP2) between the lowest CS conformer of proline and the clearly favored SB structure. 相似文献
78.
Letzel M Kirchhoff D Grützmacher HF Stein D Grützmacher H 《Dalton transactions (Cambridge, England : 2003)》2006,(16):2008-2016
The unimolecular reactions of radical cations and cations derived from phenylarsane, C6H5AsH2 (1) and dideutero phenylarsane, C6H5AsD2 (1-d2), were investigated by methods of tandem mass spectrometry and theoretical calculations. The mass spectrometric experiments reveal that the molecular ion of phenylarsane, 1*+, exhibits different reactivity at low and high internal excess energy. Only at low internal energy the observed fragmentations are as expected, that is the molecular ion 1*+ decomposes almost exclusively by loss of an H atom. The deuterated derivative 1-d2 with an AsD2 group eliminates selectively a D atom under these conditions. The resulting phenylarsenium ion [C6H5AsH]+, 2+, decomposes rather easily by loss of the As atom to give the benzene radical cation [C6H6]*+ and is therefore of low abundance in the 70 eV EI mass spectrum. At high internal excess energy, the ion 1*+ decomposes very differently either by elimination of an H2 molecule, or by release of the As atom, or by loss of an AsH fragment. Final products of these reactions are either the benzoarsenium ion 4*+, or the benzonium ion [C6H7]+, or the benzene radical cation, [C6H6]*+. As key-steps, these fragmentations contain reductive eliminations from the central As atom under H-H or C-H bond formation. Labeling experiments show that H/D exchange reactions precede these fragmentations and, specifically, that complete positional exchange of the H atoms in 1*+ occurs. Computations at the UMP2/6-311+G(d)//UHF/6-311+G(d) level agree best with the experimental results and suggest: (i) 1*+ rearranges (activation enthalpy of 93 kJ mol(-1)) to a distinctly more stable (DeltaH(r)(298) = -64 kJ mol(-1)) isomer 1 sigma*+ with a structure best represented as a distonic radical cation sigma complex between AsH and benzene. (ii) The six H atoms of the benzene moiety of 1 sigma*+ become equivalent by a fast ring walk of the AsH group. (iii) A reversible isomerization 1+<==>1 sigma*+ scrambles eventually all H atoms over all positions in 1*+. The distonic radical cation 1*+ is predisposed for the elimination of an As atom or an AsH fragment. The calculations are in accordance with the experimentally preferred reactions when the As atom and the AsH fragment are generated in the quartet and triplet state, respectively. Alternatively, 1*(+) undergoes a reductive elimination of H2 from the AsH2 group via a remarkably stable complex of the phenylarsandiyl radical cation, [C6H5As]*+ and an H2 molecule. 相似文献
79.
Dirk T.S. Rijkers Fernando de Prada LópezRob M.J. Liskamp François Diederich 《Tetrahedron letters》2011,52(51):6963-6967
We report on the chemoselective coupling between colorless peptide fragments functionalized with a mutually reactive electron-rich Nα-(4-ethynylphenyl)-Nα-(methyl)-glycyl- and an electron-deficient [4-(2,2-dicyanovinyl)]benzoyl moiety. The resulting donor-substituted 1,1-dicyanobuta-1,3-dienes represent a new class of orange-red colored (λmax = 450-500 nm, with molar extinction coefficients (ε) above 5,000 mol−1 dm3 cm−1) peptide-based imaging chromophores. 相似文献
80.