DFT calculations of 29Si-NMR chemical shifts in Ru(II) silyl complexes. Searching for trends and accurate values.

Amalia Poblador-Bahamonde (1) , Romuald Poteau (2) , Christophe Raynaud (1) , Odile Eisenstein (1)

1 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
2 LPCNO - Laboratoire de physique et chimie des nano-objets

The 29Si chemical shifts in a series of closely related Ru(II) silyl complexes have been calculated by DFT methods and compared to the experimental values. The factors that lead to possible discrepancies between experimental and calculated values have been identified. It is shown that it is necessary to include the spin-orbit coupling associated with the relativistic effects of the heavy atoms for quantitative agreement with observed chemical shifts but trends are reasonably reproduced when the calculations do not include this correction. An NBO analysis of the NMR contributions from the bonds to Si and the Si core shows the greater importance of the former and a fine tuning originating from the latter.

Domaines: Chimie théorique et/ou physique; Chimie de coordination

Amalia Poblador-Bahamonde, Romuald Poteau, Christophe Raynaud, Odile Eisenstein. DFT calculations of 29Si-NMR chemical shifts in Ru(II) silyl complexes. Searching for trends and accurate values.. Dalton Transactions, 2011, 40 (42), pp.11321 - 11326. ⟨10.1039/C1DT11135C⟩. ⟨hal-00633440⟩