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Inside Cover: Understanding the Mechanisms of Unusually Fast HH, CH, and CC Bond Reductive Eliminations from Gold(III) Complexes (Chem. Eur. J. 45/2014)
Author(s) -
Nijamudheen A.,
Karmakar Sharmistha,
Datta Ayan
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Reports
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201490187
Subject(s) - chemistry , quantum tunnelling , kinetic isotope effect , reductive elimination , kinetic energy , cover (algebra) , transition metal , computational chemistry , quantum , atomic physics , physics , catalysis , condensed matter physics , quantum mechanics , organic chemistry , mechanical engineering , deuterium , engineering
DFT calculations explain the unprecedented rapid CC bond reductive elimination for gold complexes like cis ‐[Ph 3 PAu(4‐F‐C 6 H 4 ) 2 ]Cl. Metal–carbon bond strengths in the transition states due to the effective orbital interactions were found to play a decisive role. Quantum mechanical tunneling (QMT) is shown to assist the reaction at ambient temperatures. The tunneling contribution leads to large primary kinetic isotope effects (KIE) and a strong violation of the rule of geometric mean of the primary and secondary KIE. For more details, see the Full Paper by A. Datta and co‐workers on page 14650 ff.