Experimental Sector
Computation details: All DFT calculations were accomplished with
Gaussian 09[19] program package using B3LYP
functional. 6-31G* basis set were used for all atoms except for Cr,
which was described with LANL2DZ (ECP) basis
set[20]. The Gaussian View 6.0 program was used to
build the structures. Monovalent cations with quartet spin states were
considered in theoretical models for the DFT
study[21]. Vibrational frequencies were checked
for all minima and transition states. Intrinsic reaction coordinate
calculations were carried out to verify connections between transition
states and different conformations. The model chosen was
Cr/Me2PN(C5H9)PMe2with a cyclopentyl group attached to N, and the formation of active
cationic Cr(I) specie includes reduction implication of cocatalyst from
Cr(III). The Gibbs free energy collected under default conditions, and
the solvent used in the calculation is methylcyclohexane.
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