Journal of inclusion phenomena

, Volume 4, Issue 4, pp 415–427 | Cite as

Competition among aromatic guests for the host tetrakis(4-methylpyridine)nickel(II) isothiocyanate and a basis for the observed selectivity

  • Harvey L. Wiener
  • Lee Ilardi
  • Patricia Liberati
  • Lisa Dengler
  • Sheryl A. Jeffas
  • Shahrokh Saba
  • Norman O. Smith


In continuing attempts to determine the basis for the selectivity shown by the host Ni(4-mepy)4(NCS)2 (1) toward aromatic guests, distribution data between solid and liquid phases are reported for seven ternary systems at room temperature. These consist of1,p-xylene, and each of the following:p-bromotoluene,p-chlorotoluene,p-fluorotoluene,p-dichlorobenzene, benzene, and 4-methylpyridine, as well as the system1-p-chlorotoluene-p-dichlorobenzene. The results, as well as those for five systems already published, have been reviewed and a hierarchy of selectivity developed. After correcting the observed selectivity for inequality of guest vapour pressures the order of decreasing preference is found to bep-bromotoluene >p-dichlorobenzene >p-chlorotoluene > deuterated and protiatedp-xylenes > ethylbenzene > 4-methylpyridine >p-fluorotoluene > toluene > benzene. With the exception of 4-methylpyridine, this is the same as the order of decreasing van der Waals length of the guest molecule and, where known, the order of enthalpy of inclusion. Although longer guest molecules and those with higher vapour pressures are favoured in selectivity, guests with longer molecules are likely to have lower vapour pressures. The activity coefficients of the included guests are calculated assuming that the liquid phases follow Raoult's law.

Key words

Selectivity of guests Ni(4-mepy)4(NCS)2 van der Waals length 


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Copyright information

© D. Reidel Publishing Company 1986

Authors and Affiliations

  • Harvey L. Wiener
    • 1
  • Lee Ilardi
    • 1
  • Patricia Liberati
    • 1
  • Lisa Dengler
    • 1
  • Sheryl A. Jeffas
    • 1
  • Shahrokh Saba
    • 1
  • Norman O. Smith
    • 1
  1. 1.Department of ChemistryFordham UniversityBronxUSA

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