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.

1,4-Addition of a Terminal Phosphinidene Complex to [5]Metacyclophane.

Three novel aspects emerge for the reaction of [5]metacyclophane (1) with the (intermediate) phenylphosphinidene complex 2 to give the 7-phosphanorbornadiene 3. It is the first 1,4-addition of a phosphinidene complex to an unsaturated system, the first addition of a phosphinidene complex to a benzene ring, and the first [4+1] cycloaddition to an aromatic compound.