title: Photochemistry of a Puckered Ferracyclobutadiene in Liquid Solution Studied by Time-Resolved Fourier-Transform Infrared Spectroscopy.
abstract: Flash photolysis combined with step-scan and rapid-scan Fourier-transform infrared spectroscopy was carried out to explore the photochemistry of a puckered, quasi-square pyramidal ferracyclobutadiene, [Fe{κ(2) -C3 (NEt2 )3 }(CO)3 ]BF4 ([1]BF4 ), that features three additional carbonyl ligands in the metal coordination sphere. In liquid solution at room temperature, an excitation with λ=355 nm light resulted in the loss of one CO ligand, which is cleaved from a basal metal-coordination site. Within the time resolution of the experiment, a solvent molecule promptly refills the resultant vacancy at the coordinatively unsaturated metal center. In the weakly interacting liquid, dichloromethane, the counterion of the complex is subsequently able to substitute the solvent in the coordination sphere of the iron center, thereby forming as a stable product a neutral dicarbonyl tetrafluoroborato iron(0) species containing a four-membered ferracycle.
authors.affiliation: Institut für Physikalische und Theoretische Chemie, der Rheinischen Friedrich-Wilhelms-Universität, Wegelerstrasse 12, 53115 Bonn (Germany).
authors.forename: Joel
authors.initials: J
authors.lastname: Torres-Alacan
authors.affiliation: Institut für Anorganische Chemie, der Rheinischen Friedrich-Wilhelms-Universität, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Ujjal
authors.initials: U
authors.lastname: Das
authors.affiliation: Institut für Physikalische und Theoretische Chemie, der Rheinischen Friedrich-Wilhelms-Universität, Wegelerstrasse 12, 53115 Bonn (Germany).
authors.forename: Boris
authors.initials: B
authors.lastname: Wezisla
authors.affiliation: Institut für Anorganische Chemie, der Rheinischen Friedrich-Wilhelms-Universität, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Martin
authors.initials: M
authors.lastname: Straßmann
authors.affiliation: Institut für Anorganische Chemie, der Rheinischen Friedrich-Wilhelms-Universität, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors.forename: Alexander C
authors.initials: AC
authors.lastname: Filippou
authors.affiliation: Institut für Physikalische und Theoretische Chemie, der Rheinischen Friedrich-Wilhelms-Universität, Wegelerstrasse 12, 53115 Bonn (Germany). p.voehringer@uni-bonn.de.
authors.forename: Peter
authors.initials: P
authors.lastname: Vöhringer
keywords: metallacycles; metathesis; photochemistry; time-resolved vibrational spectroscopy; transition-metal complexes