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Updated: Feb 23, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Is the R3 Si Moiety in Metal-Silyl Complexes a Z ligand? An Answer from the Interaction Energy
Dang Ho Binh1, Milan Milovanović1,2, Julia Puertes-Mico1
1Institut de Chimie de Strasbourg UMR7177, Université de Strasbourg, 4, rue Blaise Pascal, 67000, Strasbourg, France.
Abstract:
The computation of metal-silyl interaction energies indicates the existence of situations in which the silyl group behaves as a Z-type ligand according to the Green method of covalent-bond classification. There is a scale of relative intrinsic silylicity Π, defined as the ratio of the intrinsic silyl-to-triflate interaction energy of a silyltriflate as a reference compound relative to the silyl-to-metal interaction of given complex, that can reveal in a straightforward manner the propensity of SiR3 groups to behave chemically as metal-bound "silylium" ions, namely, [SiR3 ]+ . Emblematic cases, either taken from the Cambridge Structural Database (CSD) or constructed for the purpose of this study, were also investigated from the viewpoints of extended transition-state natural orbitals for chemical valence (ETS-NOCV) and quantum theory of atoms in molecules (QTAIM) analyses. It is shown in the case of POBMUP-which is the iridium 1,3-bis[(di-tert-butylphosphino)oxy]benzene (POCOP) complex isolated by Brookhart et al.-how slight variations of molecular charge and structure can drastically affect the relative intrinsic silylicity of the SiEt3 group that is weakly bonded to the hydrido-iridium motif.
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