Complexation of crown ethers with neutral molecules. 2. Comparison of free macrocycles and their complexes with malononitrile in solution

Journal Article · Wed Aug 20 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00277a035· OSTI ID:5332106

van Staveren, C J; Aarts, V M.L.J.; Grootenhuis, P D.J.; van Eerden, J; Harkema, S; Reinhoudt, D N

Thermodynamic parameters for the complexation of a neutral guest (malononitrile) with crown ethers having ring sizes of 15 to 33 ring atoms and various functionalities were obtained. The results give useful information about the conformations of the free crown ethers and their interactions with solvent molecules. 18-Membered macrocycles form the most stable complexes with malononitrile. Crown ethers in which the uncomplexed form strong intraannular interactions are present form weaker complexes while macrocycles in which additional binding sites (e.g., C=O) are available for complexation form more stable complexes with malononitrile than expected. A compensating effect of T ..delta.. S/sup 0/ and ..delta.. H/sup 0/ of complexation was found for all complexes. The crystal structure of 2,6-pyrido-18-crown-6-CH/sub 2/(CN)/sub 2/ (1:2) was determined; it shows a hydrogen bond to the pyridyl nitrogen atom.

• Research Organization: Twente Univ. of Technology, AE Enschede, Netherlands
• OSTI ID: 5332106
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:17; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALCOHOLS
COMPLEXES
CONFIGURATION INTERACTION
DATA
EXPERIMENTAL DATA
GLYCOLS
HYDROXY COMPOUNDS
INFORMATION
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
PHYSICAL PROPERTIES
POLYETHYLENE GLYCOLS
POLYMERS
SOLVENTS
THERMODYNAMIC PROPERTIES
THERMODYNAMICS