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Updated: Mar 22, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium
Holger Braunschweig1, Alexander Damme2, Rian D Dewhurst2
1Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany. h.braunschweig@uni-wuerzburg.de.
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.
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