Computational Chemistry

Stability of Pentaorganylsilicates

I have performed quantum chemical calculations to explain the extraordinary stability of specific pentaorganylsilicates. Bond energy decompositions with ADF pointed out the special role of the bidentate biaryl moieties. These substituents are σ-electron withdrawing and sterically undemanding, which stabilizes silicon hypercoordination. Due to their π-electron richness, the biaryl groups have a strong preference to bridge one axial and one equatorial site. The fifth hydrocarbyl moiety then occupies an equatorial position, where it is bound more strongly than in an axial position.

Electronic Structure and Stability of Pentaorganosilicates

This research was published in the Journal of the American Chemical Society


Principal Stereomutation Mechanisms

Recently, I extended the insights into the fluxionality of pentaorganylsilicates to other pentacoordinate compounds, including transition-metal complexes. I developed a method to unambiguously determine the principal mechanisms of stereomutation from computed reaction pathways, which also gives a straightforward interpretation of any constraints imposed by the substituents. The results resolve a long-standing confusion over which interchange mechanisms are true alternatives. Specifically, the Berry pseudorotation and turnstile rotation mechanisms are shown to be equivalent. We propose to reassign the name "turnstile rotation" to an alternative mechanism involving cyclic permutation of three neighbouring ligands, which does resemble the motion of a three-arm turnstile gate (see below). Animations of the different mechanisms can be viewed here.

Stereomutation of Pentavalent Compounds

>> This research recently appeared in the Journal of the American Chemical Society <<


Work in Progress

Currently, I am investigating the nature of metal−ligand bonding in organometallic intermediates. Furthermore, I am calculating the reaction pathways for a homogeneous catalyst system. More will follow as soon as these results are finalized.