title: Gas-Phase Characterization of Unhindered Silanimines by Photoelectron Spectroscopy: Experimental and Theoretical Study of the Si=N Double Bond(1).
abstract: The coupling of flash vacuum thermolysis reactions (retro [2+2] cleavages) with photoelectron spectroscopy allowed the first direct characterization of several highly reactive N-alkylated silanimines. For the trimethylsilanimine 1b, the IPs corresponding to the ejection of an electron from the nitrogen lone pair (n(N)) and the pi(Si)(=)(N) orbital are observed at 7.9 and 8.3 eV, respectively. In the case of the N-isopropylated and N-tert-butylated analogues 1c,d, these characteristic ionizations are energetically closed (7.8 and 7.4 eV). These unexpected attributions have been corroborated by the ab initiocalculations of the ionization energies using 6-31G(d) and LANL1DZ basis sets and MP2 level. Our results have been completed by the determination of the structural and electronic characteristics of these silanimines.
authors.affiliation: Université de Pau et des Pays de l'Adour, Laboratoire de Physico-Chimie Moléculaire, URA CNRS 474, Avenue de l'Université, 64000 Pau, France, and ISMRA, Université de Caen, Laboratoire de Chimie Moléculaire et Thioorganique, URA CNRS 480, 14050 Caen, France.
authors.forename: V.
authors.initials: V
authors.lastname: Metail
authors.forename: S.
authors.initials: S
authors.lastname: Joanteguy
authors.forename: A.
authors.initials: A
authors.lastname: Chrostowska-Senio
authors.forename: G.
authors.initials: G
authors.lastname: Pfister-Guillouzo
authors.forename: A.
authors.initials: A
authors.lastname: Systermans
authors.forename: J. L.
authors.initials: JL
authors.lastname: Ripoll