title: Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation.
abstract: The reaction of the salts K[Ru(CO)3 (PMe3 )(SiR3 )] (R=Me, Et) with Br2 BDur or Cl2 BDur (Dur=2,3,5,6-Me4 C6 H) leads to both boryl and borylene complexes of divalent ruthenium, the former through simple salt elimination and the latter through subsequent CO loss and 1,2-halide shift. The balance of products can be altered by varying the reaction conditions; boryl complexes can be favored by the addition of CO, and borylene complexes by removal of CO under vacuum. All of these products are in competition with the corresponding (aryl)(halo)(trialkylsilyl)borane, a reductive elimination product. The Ru(II) borylene products and the mechanisms that form them are distinctly different from the analogous reactions with iron, which lead to low-valent borylene complexes, highlighting fundamental differences in oxidation state preferences between iron and ruthenium.
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany. 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.
authors.forename: Alexander
authors.initials: A
authors.lastname: Damme
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
authors.forename: Rian D
authors.initials: RD
authors.lastname: Dewhurst
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Radacki
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
authors.forename: Felix
authors.initials: F
authors.lastname: Weißenberger
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
authors.forename: Benedikt
authors.initials: B
authors.lastname: Wennemann
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
authors.forename: Qing
authors.initials: Q
authors.lastname: Ye
keywords: boryl complexes; borylene complexes; iron; ruthenium; silyl complexes