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Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation
Author(s) -
Braunschweig Holger,
Damme Alexander,
Dewhurst Rian D.,
Radacki Krzysztof,
Weißenberger Felix,
Wennemann Benedikt,
Ye Qing
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601602
Subject(s) - ruthenium , chemistry , borane , medicinal chemistry , divalent , oxidation state , photochemistry , metal , organic chemistry , catalysis
The reaction of the salts K[Ru(CO) 3 (PMe 3 )(SiR 3 )] (R=Me, Et) with Br 2 BDur or Cl 2 BDur (Dur=2,3,5,6‐Me 4 C 6 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.