title: Unraveling the Amine-Induced Disproportionation Reaction of Perchlorinated Silanes-A DFT Study.
abstract: A detailed quantum-chemical study on the amine-induced disproportionation reaction of perchlorinated silanes to neo-Si5 Cl12 is reported. The key intermediate in the resulting mechanistic scenario is a dichlorosilylene amine adduct, which is in tune with recent experimental findings. Yet, at variance with the generally accepted notion of silicon-chain growth by concerted silylene insertion into Si-Cl bonds of lower silanes, the formation of neo-Si5 Cl12 follows more complex pathways. The reactivity is dominated by the Lewis-base character of the dichlorosilylene amine adduct and characterized by three elementary steps that bear close resemblance to the key elementary steps identified earlier for the chloride-induced disproportionation of Si2 Cl6 . NBO and QTAIM analyses of the key reactive species SiCl2 ⋅NMe3 and SiCl3 (-) provide a rationale for these striking similarities.
authors.affiliation: Institut für Anorganische Chemie, Goethe-Universität, Max-von-Laue-Straße 7, 60438, Frankfurt/Main, Germany.
authors.forename: Julia I
authors.initials: JI
authors.lastname: Schweizer
authors.affiliation: Institut für Anorganische Chemie, Goethe-Universität, Max-von-Laue-Straße 7, 60438, Frankfurt/Main, Germany.
authors.forename: Lioba
authors.initials: L
authors.lastname: Meyer
authors.affiliation: Institut für Anorganische Chemie, Goethe-Universität, Max-von-Laue-Straße 7, 60438, Frankfurt/Main, Germany.
authors.forename: Andor
authors.initials: A
authors.lastname: Nadj
authors.affiliation: Institut für Anorganische Chemie, Goethe-Universität, Max-von-Laue-Straße 7, 60438, Frankfurt/Main, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Diefenbach
authors.affiliation: Institut für Anorganische Chemie, Goethe-Universität, Max-von-Laue-Straße 7, 60438, Frankfurt/Main, Germany. Max.Holthausen@chemie.uni-frankfurt.de.
authors.forename: Max C
authors.identifier: http://orcid.org/0000-0001-7283-8329
authors.initials: MC
authors.lastname: Holthausen
keywords: bonding analysis; density functional theory; disproportionation reactions; reaction mechanisms; silylenes