Structure & bonding in complexes of zero-valent heavier group 14 elements

J. Turek
Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel, Bruxelles, Belgique
Mercredi 8 Mars 2017, 11h00
bibliothèque LCT, tour 12 - 13, 4^ème étage

The research in the field of heavier low-valent Group 14 elements has not only produced various interesting compounds [1], but has also made it possible to demonstrate that some of these low-valent Group 14 derivatives can activate small molecules under mild conditions and display promising catalytic properties for future applications [2]. Among the low-valent Group 14 derivatives, monoatomic zero oxidation state complexes, the tetrylones, are perhaps the most fascinating [3].
A real breakthrough came very recently with the first published silylone and germylone reported by Roesky and Frenking (Fig. 1). Shortly after that, Driess published other examples of cyclic sila- and germadicarbenes stabilized by the chelating bis-carbene ligand. On the other hand, the sole example of a stannylone, which was published by Fischer, is stabilized by the use of only one chelating pyridine ligand.

[Picture]

Figure 1. Structure of the first characterized silylone and germylone.

The main objective of the presented work is a theoretical investigation of the structure and bonding of a series of compounds, where the heavier group 14 atoms are present with a formal oxidation state of 0. Maximum Probability Domains and Valence Bond methods were used to provide a more fundamental understanding of the L→E bonding in tetrylones.

The financial support of the Research Foundation - Flanders (FWO), under the FWO Pegasus Marie Curie fellowship scheme (Project Nr. 12T6615N) is gratefully acknowledged. _________________________________

References :
[1] (a) Y. Mizuhata, T. Sasamori, N. Tokitoh, Chem. Rev. 2009, 109, 3479 ; (b) C. Jones, Coord. Chem. Rev. 2010, 254, 1273 ; (c) M. Asay, C. Jones, M. Driess, Chem. Rev. 2011, 111, 354.
[2] P. P. Power, Nature 2010, 463, 171.
[3] G. Frenking, R. Tonner, S. Klein, N. Takagi, T. Shimizu, A. Krapp, K. K. Pandey, P. Parameswaran, Chem. Soc. Rev. 2014, 43, 5106.