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Braunschweig H, Damme A, Dewhurst RD, et al. Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation. Chemistry. 2016;22(25):8471-4doi: 10.1002/chem.201601602.
Braunschweig, H., Damme, A., Dewhurst, R. D., Radacki, K., Weißenberger, F., Wennemann, B., & Ye, Q. (2016). Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation. Chemistry (Weinheim an der Bergstrasse, Germany), 22(25), 8471-4. https://doi.org/10.1002/chem.201601602
Braunschweig, Holger, et al. "Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 22,25 (2016): 8471-4. doi: https://doi.org/10.1002/chem.201601602
Braunschweig H, Damme A, Dewhurst RD, Radacki K, Weißenberger F, Wennemann B, Ye Q. Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation. Chemistry. 2016 Jun 13;22(25):8471-4. doi: 10.1002/chem.201601602. Epub 2016 May 09. PMID: 27124888.
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Chemistry. 2016 Jun 13;22(25):8471-4. doi: 10.1002/chem.201601602. Epub 2016 May 09.

Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation.

Chemistry (Weinheim an der Bergstrasse, Germany)

Holger Braunschweig, Alexander Damme, Rian D Dewhurst, Krzysztof Radacki, Felix Weißenberger, Benedikt Wennemann, Qing Ye

Affiliations

  1. Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany. [email protected].
  2. Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.

PMID: 27124888 DOI: 10.1002/chem.201601602

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.

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: boryl complexes; borylene complexes; iron; ruthenium; silyl complexes

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