Rational design of iron catalysts for C-X bond activation.

We have quantum chemically studied the iron-mediated CX bond activation (X = H, Cl, CH ) by d -FeL complexes using relativistic density functional theory at ZORA-OPBE/TZ2P. We find that by either modulating the electronic effects of a generic iron-catalyst by a set of ligands, that is, CO, BF, PH , BN(CH ) , or by manipulating structural effects through the introduction of bidentate ligands, that is, PH (CH ) PH with n = 6-1, one can significantly decrease the reaction barrier for the CX bond activation. The combination of both tuning handles causes a decrease of the CH activation barrier from 10.