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21.
22.
Synthesis and characterization of {Ni(NO)}10 and {Co(NO)2}10 complexes supported by thiolate ligands
Nitric oxide is an important molecule in biology and modulates a variety of physiological and pathophysiological processes. Some of its regulatory functions are exerted through interactions with redox-active elements, including iron, nickel, cobalt, and sulfur. Metalloenzymes containing [ nFe- nS] ( n = 2 or 4) clusters can be activated or inactivated by reaction with NO, affording dinitrosyl iron complexes. Studies of the NO chemistry of small-molecule iron thiolate complexes have provided insight into these biological processes and suggested probable intermediates. To explore this chemistry from a different perspective, we prepared nickel and cobalt thiolate complexes and investigated their reactions with NO and related compounds. We report here the first examples of anionic complexes containing {Ni(NO)} (10) and {Co(NO) 2} (10) units, the reactivity of which suggests possible intermediates in the interconversion of iron thiolate nitrosyl compounds. Our results demonstrate new chemistry involving NO and simple complexes of nickel and cobalt supported by thiolates, which have been known for more than 30 years. The use of mass balance methodology was key to their discovery. Among the novel complexes reported are (Et 4N) 2[Ni(NO)(SPh) 3] ( 2), from (Et 4N) 2[Ni(SPh) 4] ( 1) and NO, (Et 4N) 2[Ni 2(NO) 2(mu-SPh) 2(SPh) 2] ( 3), from 1 and NO (+) or 2 and Me 3O (+), (Et 4N)[Co(NO) 2(SPh) 2] ( 5), from (Et 4N) 2[Co(SPh) 4] ( 4) and NO, and [Co 3(NO) 6(mu-SPh) 3] ( 6), from 5 and Me 3O (+). In the syntheses of 2 and 5, NO could be replaced by the convenient solid Ph 3CSNO. 相似文献
23.
T. Yu. Chesnokova B.A. Voronin A.V. Kozodoev J. Tennyson 《Journal of Molecular Spectroscopy》2009,256(1):41-44
A comparison of the atmospheric absorption calculated with different data banks of water vapour absorption lines is made. The HITRAN database, Barber-Tennyson line list (BT2), calculation of Partridge and Schwenke (PS) are considered. The contribution of H2O lines, absent in HITRAN, to the atmospheric transmission, calculated with 10 cm−1 spectral resolution in the 10 000-20 000 cm−1 spectral region is up to 1.5% for a vertical path and 4% for a solar zenith angle of 70 deg. The highest difference is observed in the 940 nm band. The incoming fluxes of solar radiation, measured by a rotating solar spectroradiometer, were modeled with BT2 and HITRAN database. The difference between measured and calculated fluxes does not exceed the instrumental uncertainties. 相似文献
24.
Jonathan Tennyson Peter F. Bernath Linda R. Brown Alain Campargue Michel R. Carleer Attila G. Császár Robert R. Gamache Joseph T. Hodges Alain Jenouvrier Olga V. Naumenko Oleg L. Polyansky Laurence S. Rothman Robert A. Toth Ann Carine Vandaele Nikolai F. Zobov Ludovic Daumont Alexander Z. Fazliev Tibor Furtenbacher Iouli E. Gordon Semen N. Mikhailenko Sergei V. Shirin 《Journal of Quantitative Spectroscopy & Radiative Transfer》2009,110(9-10):573-596
25.
Barletta P Shirin SV Zobov NF Polyansky OL Tennyson J Valeev EF Császár AG 《The Journal of chemical physics》2006,125(20):204307
The high accuracy ab initio adiabatic potential energy surfaces (PESs) of the ground electronic state of the water molecule, determined originally by Polyansky et al. [Science 299, 539 (2003)] and called CVRQD, are extended and carefully characterized and analyzed. The CVRQD potential energy surfaces are obtained from extrapolation to the complete basis set of nearly full configuration interaction valence-only electronic structure computations, augmented by core, relativistic, quantum electrodynamics, and diagonal Born-Oppenheimer corrections. We also report ab initio calculations of several quantities characterizing the CVRQD PESs, including equilibrium and vibrationally averaged (0 K) structures, harmonic and anharmonic force fields, harmonic vibrational frequencies, vibrational fundamentals, and zero-point energies. They can be considered as the best ab initio estimates of these quantities available today. Results of first-principles computations on the rovibrational energy levels of several isotopologues of the water molecule are also presented, based on the CVRQD PESs and the use of variational nuclear motion calculations employing an exact kinetic energy operator given in orthogonal internal coordinates. The variational nuclear motion calculations also include a simplified treatment of nonadiabatic effects. This sophisticated procedure to compute rovibrational energy levels reproduces all the known rovibrational levels of the water isotopologues considered, H(2) (16)O, H(2) (17)O, H(2) (18)O, and D(2) (16)O, to better than 1 cm(-1) on average. Finally, prospects for further improvement of the ground-state adiabatic ab initio PESs of water are discussed. 相似文献
26.
R-matrix calculations on electron collisions with the purine bases found in DNA and RNA (i.e., adenine and guanine) are presented. Resonant anion states of these systems are identified by employing different approximation levels of ab initio theoretical methods, such as the static exchange, the static exchange plus polarization, and the close-coupling methods. The results are compared with other available calculations and experiments. All of these ab initio approximations, which we refer to as a scattering "model," give four shape resonances of (2)A' (π) symmetry within the energy range of 10 eV for both molecules. For adenine, the most sophisticated method, the close-coupling model, gives two very narrow (2)A' (σ) symmetry Feshbach-type resonances at energies above 5 eV. Quantitative results for the total elastic and electronic excitation cross sections are also presented. 相似文献
27.
A general, full-dimensional computational method for the accurate calculation of rotationally and vibrationally excited states of tetra-atomic molecules is further developed. The resulting computer program may be run in serial and parallel modes and is particularly appropriate for molecules executing wide-amplitude motions and isomerizations. An application to the isomerizing acetylene/vinylidene system is presented. Large-scale calculations using a coordinate system based on orthogonal satellite vectors have been performed in six dimensions and vibrational term values and wave functions for acetylene and vinylidene states up to approximately 23 000 cm(-1) above the potential minimum have been determined. This has permitted the characterization of acetylene and vinylidene states at and above the isomerization barrier. These calculations employ more extensive vibrational basis sets and hence consider a much higher density of states than in any variational calculations reported hitherto for this system. Comparison of the calculated density of states with that determined empirically suggests that our calculations are the most realistic achieved for this system to date. Indeed more states have been converged than in any previous study of this system. Calculations on lower lying excited states of acetylene based on HC-CH diatom-diatom coordinates give nearly identical results to those based on orthogonal satellite vectors. Comparisons are also made with calculations based on HH-CC diatom-diatom coordinates. 相似文献
28.
29.
Andrew G. Tennyson Dr. Robert J. Ono Todd W. Hudnall Dr. Dimitri M. Khramov Dr. Joyce A. V. Er Justin W. Kamplain Dr. Vincent M. Lynch Dr. Jonathan L. Sessler Prof. Christopher W. Bielawski Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(1):304-315
Reaction of bromanil with N,N′‐dimesitylformamidine followed by deprotonation with NaN(SiMe3)2 afforded 1,1′,3,3′‐tetramesitylquinobis(imidazolylidene) ( 1 ), a bis(N‐heterocyclic carbene) (NHC) with two NHC moieties connected by a redox active p‐quinone residue, in 72 % yield of isolated compound. Bimetallic complexes of 1 were prepared by coupling to FcN3 ( 2 ) or FcNCS ( 3 ; Fc=ferrocenyl) or coordination to [M(cod)Cl] ( 4 a or 4 b , where M=Rh or Ir, respectively; cod=1,5‐cyclooctadiene). Treatment of 4 a and 4 b with excess CO(g) afforded the corresponding [M(CO)2Cl] complexes 5 a and 5 b , respectively. Analysis of 2 – 5 by NMR spectroscopy and X‐ray diffraction indicated that the electron‐deficient quinone did not significantly affect the inherent spectral properties or coordination chemistry of the flanking imidazolylidene units, as compared to analogous NHCs. Infrared spectroscopy and cyclic voltammetry revealed that decreasing the electron density at MLn afforded an increase in the stretching energy and a decrease in the reduction potential of the quinone, indicative of metal–quinone electronic interaction. Differential pulse voltammetry and chronoamperometry of the metal‐centered oxidations in 2 – 4 revealed two single, one‐electron peaks. Thus, the metal atoms bound to 1 are oxidized at indistinguishable potentials and do not appear electronically coupled. However, the metal–quinone interaction was used to increase the electron density at coordinated metal atoms. Infrared spectroelectrochemistry revealed that the average νCO values for 5 a and 5 b decreased by 14 and 15 cm?1, respectively, upon reduction of the quinone embedded within 1 . These shifts correspond to 10 and 12 cm?1 decreases in the Tolman electronic parameter of this ditopic ligand. 相似文献
30.
Jonathan Tennyson Peter F. Bernath Alain Campargue Ludovic Daumont Joseph T. Hodges Oleg L. Polyansky Laurence S. Rothman Ann Carine Vandaele Sophie Fally Tibor Furtenbacher Shui-Ming Hu Boris A. Voronin 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(15):2160-1106
This is the second of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD16O, HD17O, and HD18O. The MARVEL (measured active rotational-vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0-22 708, 0-1674, and 0-12 105 cm−1 for HD16O, HD17O, and HD18O, respectively. For HD16O, 54 740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36 690 distinct assignments and 8818 energy levels. For HD17O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD18O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD16O at 296 K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. In addition, the transition and energy level information for H217O and H218O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573-96], has been updated. 相似文献