title: Side-on bridging coordination of N2: spectroscopic characterization of the planar Zr2N2 core and theoretical investigation of its butterfly distortion.
abstract: The vibrational and electronic structure of the side-on N(2)-bridged Zr complex [((P(2)N(2))Zr)(2)(mu-eta(2):eta(2)-N(2))] (P(2)N(2)=PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh) were analyzed. The vibrational characterization of the planar Zr(2)N(2) core was based on resonance Raman and infrared spectroscopy. In the Raman spectrum, the Nbond;N stretching band is found at 775 cm(-1) with an isotope shift of 22 cm(-1). Due to its appearance in many overtones and combination modes, the metal-metal stretch is assigned to the peak at 295 cm(-1). The two ungerade modes of the Zr(2)N(2) core were identified in the infrared spectrum. Based on these four vibrations of the Zr(2)N(2) unit, a quantum chemical assisted normal coordinate analysis (QCA-NCA) was performed. The force constants for the N--N and Zr--N bonds were calculated to be 1.53 and 2.58 mdyn A(-1), respectively. The butterfly distortion of the Zr(2)N(2) unit obtained in DFT geometry optimizations of planar side-on N(2)-bridged Zr complexes was analyzed in more detail. It was found that on bending of the Zr(2)N(2) core, the lone pairs of the axial amide ligands are rotated by 90 degrees. The bent Zr(2)N(2) unit is 11 kcal mol(-1) lower in energy than the planar core due to a more uniform distribution of electron density between the metal atoms and N(2) and delocalization of electron density from the amide ligands to the Zr(2)N(2) unit. The spectroscopic implications of this distortion are analyzed.
authors.affiliation: Institut für Anorganische Chemie Christian Albrechts Universität Kiel Ohlshausenstrasse 40, 24098 Kiel, Germany.
authors.forename: Felix
authors.initials: F
authors.lastname: Studt
authors.forename: Lara
authors.initials: L
authors.lastname: Morello
authors.forename: Nicolai
authors.initials: N
authors.lastname: Lehnert
authors.forename: Michael D
authors.initials: MD
authors.lastname: Fryzuk
authors.forename: Felix
authors.initials: F
authors.lastname: Tuczek