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Volumn 10, Issue 22, 2004, Pages 5730-5736

Oxidation of CS2 by AsBr4+: The unexpected formation of the simple CS2Br3+ carbenium ion

Author keywords

Arsenic; Carbenium ion; Carbon disulfide; Oxidation; Weakly coordinating anions

Indexed keywords

ARSENIC COMPOUNDS; COMPUTATIONAL METHODS; ELECTRONS; INFRARED SPECTROSCOPY; IONS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION; QUANTUM THEORY; SYNTHESIS (CHEMICAL);

EID: 9244228976     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400046     Document Type: Article
Times cited : (14)

References (54)
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    • note
    • + which resonate at δ = -292 and +97 ppm and thus far from where they are expected without relativistic contribution.
  • 33
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    • note
    • 3) groups of the anion (#2) had to be split over two positions and the disordered atoms were included isotropically in the refinement. Their position was fixed with restraints (SADI command). All other atoms were refined anisotropically. CCDC-228671 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.uk).
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    • note
    • - ion: range 145.29(19)°-149.4(2)°, 148.4(2)° (#1) and 147.2(2)° (#2) on average.
  • 38
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    • (Eds.: M. O'Keefe, A. Navrotsky), Academic Press, London
    • 0 = 1.55 Å. see: I. D. Brown, in Structure and Bonding in Crystals, Vol. 2 (Eds.: M. O'Keefe, A. Navrotsky), Academic Press, London, 1981, p. 1.
    • (1981) Structure and Bonding in Crystals, Vol. 2 , vol.2 , pp. 1
    • Brown, I.D.1
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    • note
    • 6 (not further analysed).
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    • 9244255444 scopus 로고    scopus 로고
    • note
    • z orbital at the carbenium center. The electron deficiency at S can then be removed in part by a further donation of electrons from the Br lone pair orbital to the (now only partially filled) S lone pair orbital. A similar interaction is responsible for resonance structure G, for which also no sulfur d orbital participation has to be assumed. (Diagram preseanted).
  • 43
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    • Patent, US 3331872, 1967
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    • Pitt, H.M.1    Bender, H.2
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    • note
    • Thermal and entropic contributions to the enthalpy and free energy were obtained by fully optimizing all the species in question with Gaussian 98W at the semiempirical PM3 level. All these species also represented true minima without imaginary frequencies at the PM3 level. ZPE's were taken from the MP2 calculation. Since statistic thermodynamics is only little influenced by the employed geometries and the entropic contributions mainly arise from the moment of inertia of a species, it is believed that errors associated with this procedure are very small if used consistently.


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