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Volumn 48, Issue 5, 2009, Pages 1938-1959

77Se NMR Spectroscopic, DFT MO, and VBT Investigations of the Reversible Dissociation of Solid (Se6l2)[AsF 6]2· 2SO2 in Liquid SO2 to Solutions Containing 1.4-Se6l22+ in Equilibrium with Sen2 (n = 4, 8, 10) and Seven Binary Selenium Iodine Cations: ...

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EID: 84908659805     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic8015673     Document Type: Article
Times cited : (26)

References (183)
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    • -1) is, therefore, the major factor in accounting for the instability of RSel molecules.
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    • The temperature of the sonic bath needs to be carefully controlled, because higher temperatures may lead to dangerously high pressures inside the NMR tube
    • The temperature of the sonic bath needs to be carefully controlled, because higher temperatures may lead to dangerously high pressures inside the NMR tube.
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    • In the course of this study spanning more than 10 years, both 1D and 2D NMR spectra have been recorded on a variety of instruments: VAR1AN UNITY 200 (University of New Brunswick, Bruker AM250 and AM500 (McMaster University, as well as Bruker DSX300 and DXP400 University of Oulu, All spectroscopic information is consistent with the actual spectra reported in this contribution
    • In the course of this study spanning more than 10 years, both 1D and 2D NMR spectra have been recorded on a variety of instruments: VAR1AN UNITY 200 (University of New Brunswick), Bruker AM250 and AM500 (McMaster University), as well as Bruker DSX300 and DXP400 (University of Oulu). All spectroscopic information is consistent with the actual spectra reported in this contribution.
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    • The intensity measurements were repeated by using a pulse width of 4.0 μs (nuclear tip angle of 23°) but keeping the acquisition time and relaxation delay constant. There were virtually no changes in the intensities.
    • The intensity measurements were repeated by using a pulse width of 4.0 μs (nuclear tip angle of 23°) but keeping the acquisition time and relaxation delay constant. There were virtually no changes in the intensities.
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    • Relative AIM bond orders have been determined from calculated electron densities at bond critical points by calibrating the results with respect to species with well-defined bond orders. Se-Se bonds were calibrated against bonds in (Se3Br3, and Se2Me2 and Se-I bonds against bonds in I2Se-I-SeI2, Me3CSeI. and Sel2+ according to the procedure given in ref 54
    • + according to the procedure given in ref 54.
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    • The geometry optimizations reveal that many cations show several conformations that are lying relatively close in energy. They are denoted by a set of numerals nm nindicates the identification number of the cation, as defined in the main text, and the subscript m identifies their different conformations, as shown in Figure 8
    • m (nindicates the identification number of the cation, as defined in the main text, and the subscript m identifies their different conformations, as shown in Figure 8).
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    • solv, (PBE0/COSMO).
    • solv, (PBE0/COSMO).
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    • 2+ does not readily adopt a clusterlike structure on its own in the absence of environmental effect (e.g. solvent or crystal lattice).
    • 2+ does not readily adopt a clusterlike structure on its own in the absence of environmental effect (e.g. solvent or crystal lattice).
  • 155
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    • The bond alternation can be rationalized in terms of the relative positive charge carried by the selenium atoms in question. In 1,1,4,4-Se 4I42, the four selenium atoms carry a charge of +0.86 (on the average, 0.22/Se atom, In 1,4-Se6I 22, the total charge of the six selenium atoms is +1.38 (on the average, 0.23/Se atom, Therefore, the bond alternations in both cations are similar. Se102+ shows a bicyclic structure. In the six-atomic ring fragment, the total charge of +1.38 (average +0.23/Se atom) and thus the bond alternation are very similar to those observed in both Se4I42+ and Se6I2 2, By contrast, the four-atomic fragment in Se10 2+ carries a charge of only +0.62. Therefore, there is less charge delocalization, and the fragment shows a smaller bond alternation
    • 2+ carries a charge of only +0.62. Therefore, there is less charge delocalization, and the fragment shows a smaller bond alternation.
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    • The ZORA rPBE/QZ4P NMR chemical shifts (vacuum/explicit solvent, ppm) for the low-lying conformations of selenium-iodine cations: The three conformations of 1,1,6,6-Se6I42, for the numbering of atoms, see Figure 18b] are as follows. Conformation 81: Sel 1205/995, Se2 1135/1080, Se3 1537/1423, Se4 1542/1533, Se5 1116/1105, Se6 1128/1044. Conformation 82: Sel, Se2 1217/1129, Se3, Se4 1615/1541, Se5, Se6 1128/1084. Conformation 83: Sel, Se2 1415/995, Se3, Se4 1825/1373, Se5, Se6 1372/1144. The two conformations of 1,1,6-Se6I3, for the numbering of atoms, see Figure 18c] are as follows. Conformation 91 Sel 1165/1045, Se2 1734/1638. Se3 1172/1064, Se4 1149/1044. Se5 1304/1162, Se6 1013/889. Conformation 92: Sel 1089/1057, Se2 1539/1451, Se3 1190/1114, Se4 1199/1099, Se5 1291/1145, Se6 1035/876. The four conformations of Se 7
    • 4: Sel 1061/1120, Se2 1427/1399, Se3 906/986, Se4 1400/1394. Se5 1022/999. Se6 982/1050, Se7 1063/1111.
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    • Several alternatives for the assignment of the resonance groups A-E to different cations were considered: group A, Se2I, group B, 1,2-Se 6I22, group C, 1,1,6,6-Se6I 42, asymmetric rotamer, group D, 1,4-Se 7I22, 1,1,7,7-Se7I4 2, symmetric rotamer, and Se72, group E, Se7I, 1,1,7,7-Se7I42, asymmetric rotamer, These assignments were rejected because of a poor fit between the calculated and observed chemical shifts, inconsistency with coupling information, or chemical implausibility see the Supporting Information for details
    • 2+ (asymmetric rotamer). These assignments were rejected because of a poor fit between the calculated and observed chemical shifts, inconsistency with coupling information, or chemical implausibility (see the Supporting Information for details).
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    • 54
    • 54
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    • Due to the dynamic nature of the solution environment, it would be desirable to calculate chemical shifts as statistical averages of calculations performed on a representative set of structures obtained from large-scale molecular dynamics simulations.87b
    • 87b
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    • 84908704593 scopus 로고    scopus 로고
    • 48 to be responsible for the group C resonances did not agree well with the observed resonances (see Table 5 and ref 99).
    • 48 to be responsible for the group C resonances did not agree well with the observed resonances (see Table 5 and ref 99).
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    • 77Se NMR spectrum of the final equilibrium mixture.
    • 77Se NMR spectrum of the final equilibrium mixture.
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    • It can be estimated from the recorded intensities that the uncertainty in the molar amounts is ca. 5
    • It can be estimated from the recorded intensities that the uncertainty in the molar amounts is ca. 5%.
  • 167
    • 84908704237 scopus 로고    scopus 로고
    • The values given in parentheses represent the estimated standard deviations in the molar amounts
    • The values given in parentheses represent the estimated standard deviations in the molar amounts.
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    • 77Se NMR spectroscopy taking into consideration the numerous other species that take part in the equilibrium.
    • 77Se NMR spectroscopy taking into consideration the numerous other species that take part in the equilibrium.
  • 176
    • 84908704477 scopus 로고    scopus 로고
    • The equations and reactions numbered with the prefix S refer to those given in Supporting Information.
    • The equations and reactions numbered with the prefix "S" refer to those given in Supporting Information.
  • 178
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    • 2O. The hexa- and octahydrates, whilst themselves being thermodynamically stable, do not have stable unsolvated counterparts.
    • 2O. The hexa- and octahydrates, whilst themselves being thermodynamically stable, do not have stable unsolvated counterparts.
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    • Faggiani, R.; Gillespie, R. 1; Kolis, J. W. J. Chem. Soc., Chem. Commun. 1987, 592.


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