Abstract
Recently published experimental results on a nonheme synthetic [(Bn-TPEN)Mn IVO] 2+ complex reveal that it is capable of activating strong C-H bonds. However, the final products are shown to contain Mn III instead of the expected Mn II, which should be formed if a rebound mechanism similar to what is assumed for heme Fe IVO was to occur. It was proposed that the substrate radical generated during H-abstraction dissociates from the Mn IIIOH complex and undergoes an additional reaction to a second molecule of Mn IVO, leading to Mn III. Density functional calculations reveal the root cause of why a follow-up rebound to form Mn II and alcohol is not preferred in this system. It is further shown that nonheme Mn IVO has a more complex spin-state manifold during C-H activation reactions compared with Fe IVO, and that spin-state matters in oxidative chemistry of metal-oxo reagents.
Original language | English |
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Pages (from-to) | 2851-2856 |
Number of pages | 6 |
Journal | Journal of Physical Chemistry Letters |
Volume | 3 |
Issue number | 19 |
DOIs | |
State | Published - 4 Oct 2012 |