TY - JOUR
T1 - The origins of dramatic axial ligand effects
T2 - Closed-shell Mn VO complexes use exchange-enhanced open-shell states to mediate efficient H abstraction reactions
AU - Janardanan, Deepa
AU - Usharani, Dandamudi
AU - Shaik, Sason
PY - 2012/4/27
Y1 - 2012/4/27
N2 - Spin-state effects: In [(Cz)Mn VO] complexes, even with singlet closed-shell ground states, the reactive state is the open-shell triplet B state (S B=1) that has a high oxyl radical character and a transition state (TS) stabilized by exchange-enhanced reactivity (EER; see picture). The dramatic axial ligand effect originates in the EER of this state.
AB - Spin-state effects: In [(Cz)Mn VO] complexes, even with singlet closed-shell ground states, the reactive state is the open-shell triplet B state (S B=1) that has a high oxyl radical character and a transition state (TS) stabilized by exchange-enhanced reactivity (EER; see picture). The dramatic axial ligand effect originates in the EER of this state.
KW - density functional calculations
KW - exchange-enhanced reactivity
KW - high-valent Mn-oxo
KW - hydrogen atom abstraction
UR - http://www.scopus.com/inward/record.url?scp=84860212540&partnerID=8YFLogxK
U2 - 10.1002/anie.201200689
DO - 10.1002/anie.201200689
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C2 - 22438238
AN - SCOPUS:84860212540
SN - 1433-7851
VL - 51
SP - 4421
EP - 4425
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 18
ER -