title: IR spectra of C2H5(+)-N2 isomers: evidence for dative chemical bonding in the isolated ethanediazonium ion.
abstract: The potential energy surface (PES) of C(2)H(5)(+)-N(2) is characterized in detail by infrared photodissociation (IRPD) spectroscopy of mass-selected ions in a quadrupole tandem mass spectrometer and ab initio calculations at the MP2/6-311G(2df,2pd) level. The PES features three nonequivalent minima. Two local minima, 1-N(2)(H) and 1-N(2)(C), are adduct complexes with binding energies of D(0) = 18 and 12 kJ/mol, in which the N(2) ligand is weakly bonded by electrostatic forces to either the acidic proton or the electrophilic carbon atom of the nonclassical C(2)H(5)(+) ion (1), respectively. The global minimum 3 is the ethanediazonium ion, featuring a weak dative bond of D(0) = 38 kJ/mol. This interaction strength is sufficient to switch the C(2)H(5)(+) structure from nonclassical to classical. The 1-N(2)(C) isomer corresponds to the entrance channel complex for addition of N(2) to 1 yielding the product 3. This reaction involves a small barrier of 7 kJ/mol as a result of the rearrangement of the C(2)H(5)(+) ion. The partly rotationally resolved IRPD spectrum of C(2)H(5)(+)-N(2) recorded in the C-H stretch range is dominated by four bands assigned to 3 and one weak transition attributed to 1-N(2)(H). The abundance ratio of 1-N(2)(H) and 3 estimated from the IRPD spectrum as ∼1% is consistent with the calculated free energy difference of 12 kJ/mol. As the ethanediazonium ion escaped previous mass spectrometric detection, the currently accepted value for the ethyl cation affinity of N(2) is revised from -ΔH(0) = 15.5 ± 1.5 to ∼42 kJ/mol. The first experimental identification and characterization of 3 provides a sensitive probe of the electrophilic character and fluxionality of the ethyl cation. Comparison of 3 with related alkanediazonium ions reveals the drastic effect of the size of the alkyl chain on their chemical reactivity, which is relevant in the context of hydrocarbon plasma chemistry of planetary atmospheres and the interstellar medium, as well as alkylation reactions of (bio)organic molecules (e.g., carcinogenesis and mutagenesis of DNA material).
authors.affiliation: Institut für Optik und Atomare Physik, Technische Universität Berlin, Berlin, Germany. dopfer@physik.tu-berlin.de
authors.forename: Otto
authors.initials: O
authors.lastname: Dopfer
authors.forename: Horia-Sorin
authors.initials: HS
authors.lastname: Andrei
authors.forename: Nicola
authors.initials: N
authors.lastname: Solcà
mesh_terms: D004980:Ethane / Q000031:analogs & derivatives / Q000737:chemistry* / Q000302:isolation & purification; D007477:Ions / Q000737:chemistry / Q000302:isolation & purification; D009584:Nitrogen / Q000737:chemistry* / Q000302:isolation & purification; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism
chemical_list: D007477:Ions; D004980:Ethane; D009584:Nitrogen