Matrix Isolation Infrared and ab Initio Study of the 1:1 Complexes of Cyclopentadiene with Nitrogen and Oxygen Bases: C−H···N(O) Hydrogen Bonding Involving an sp3-Hybridized Carbon

Autor:	Mark A. Hilfiker, Andrew Maynard, Cindy Samet, Erin R. Mysak
Rok vydání:	2001
Předmět:	chemistry.chemical_classification Cyclopentadiene Hydrogen Hydrogen bond Matrix isolation Ab initio chemistry.chemical_element Interaction energy Photochemistry chemistry.chemical_compound Crystallography chemistry Ab initio quantum chemistry methods Physical and Theoretical Chemistry Alkyl
Zdroj:	The Journal of Physical Chemistry A. 105:3087-3095
ISSN:	1520-5215 1089-5639
Popis:	Hydrogen-bonded complexes of cyclopentadiene with the strong bases ammonia, trimethylamine, and dimethyl ether have been isolated and characterized for the first time in argon matrices at 16 K. Coordination of the acidic alkyl hydrogen to the electron donor was evidenced by distinct red shifts of the CH 2 stretching modes of cyclopentadiene in the infrared spectrum. An additional `‚‚‚‚﷿ interaction was evidenced by the red shift of an olefinic C-H stretching mode. Ab initio calculations yield a complex with NH3 located above the ring, oriented by both of these hydrogen-bonding interactions. The calculated interaction energy of the complex is 2.40 kcal/mol, with the energy being divided equally between these two interactions. This study represents the first example of an sp 3 -hybridized carbon on a hydrocarbon taking part in a C-H‚‚‚N(O) hydrogen bond.
Databáze:	OpenAIRE
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