title: Ansa-Complexes of [Mn(η(5) -C5 H5 )(η(6) -C6 H6 )]: Preparation, Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3).
abstract: We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa-bridging elements. Their preparation was achieved by salt-elimination reactions of the dilithiated precursor [Mn(η(5) -C5 H4 Li)(η(6) -C6 H5 Li)]⋅pmdta (pmdta=N,N,N',N',N''-pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single-atom-bridged derivatives, [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] and [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SiPh2 ], could also be determined by X-ray structural analysis. We investigated for the first time the reactivity of these ansa-cyclopentadienyl-benzene manganese compounds. The reaction of the distannyl-bridged complex [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )Sn2 tBu4 ] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn-Sn bond to give a triatomic ansa-bridge. The investigation of the ring-opening polymerization (ROP) capability of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] with [Pt(PEt3 )3 ] showed that an unexpected, unselective insertion into the Cipso -Sn bonds of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] had occurred.
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623. h.braunschweig@uni-wuerzburg.de.
authors.forename: Holger
authors.initials: H
authors.lastname: Braunschweig
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Alexander
authors.initials: A
authors.lastname: Damme
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Klaus
authors.initials: K
authors.lastname: Dück
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Marco
authors.initials: M
authors.lastname: Fuß
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Christian
authors.initials: C
authors.lastname: Hörl
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Thomas
authors.initials: T
authors.lastname: Kramer
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Ivo
authors.initials: I
authors.lastname: Krummenacher
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Thomas
authors.initials: T
authors.lastname: Kupfer
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Valerie
authors.initials: V
authors.lastname: Paprocki
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
authors.forename: Christoph
authors.initials: C
authors.lastname: Schneider
keywords: ansa-complexes; manganese; sandwich complexes; synthetic methods