Hybrid Car-Parrinello/Molecular Mechanics Modelling of Transition Metal Complexes: Structure, Dynamics and Reactivity

Abstract

The theoretical modelling of chemically active transition metal (TM) centres is a notoriously difficult task. The metal-ligand interactions in these complexes are often highly directional and the concoction of suitable analytic interaction potentials can be far from trivial. The situation is rendered even more difficult by the fact that at finite temperature, the system might switch dynamically between different bonding situations or exhibit several energetically close-lying spin states which are all characterized by different coordination numbers and geometries. In this article, we describe the structural, dynamical and reactive properties of complex TM-containing systems with the help of a mixed quantum mechanical/molecular mechanical (QM/MM) molecular dynamics approach, in which the TM centre is described with generalized gradient corrected density functional theory embedded in a classical force field description. The power of such a combined Car-Parrinello/molecular mechanics approach is illustrated with a number of representative examples ranging from enantioselective TM catalysts to radiopharmaceuticals and metalloenzymes.

Dynamical Mechanism May Avoid High-Oxidation State Ir(V)–H Intermediate and Coordination Complex in Alkane and Arene C–H Activation by Cationic Ir(III) Phosphine

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“…41,42 Ab initio MD, usually based on DFT, can also handle systems in the liquid phase, even if a relatively limited number of atoms can be treated. Quantum Mechanics/Molecular Mechanics (QM/MM) simulations are a possible compromise 43,44 to go beyond these size limitations. The solute molecule, whose vibrational properties are of interest, are treated at the DFT level, thus being able to provide correct vibrational properties, whereas the solvent is treated by using classical force fields.…”