σ‐Silane Ruthenium Complexes: The Crucial Role of Secondary Interactions

Abstract The bonding coordination mode of various silanes to ruthenium complexes is discussed on the basis of a detailed analysis of NMR, IR, X‐ray and DFT data. It is now more and more obvious that a continuum exists between the two extreme situations, i.e. formation of a σ‐silane complex or Si–H bond breaking leading to oxidative addition. Within this continuum, secondary interactions involving Si and H play a significant role, in particular for the stabilization of unusual structures or as intermediates in exchange processes. Here, we highlight the criteria allowing the best description of the different bonding modes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)