Is the R 3 Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy
AuthorsBinh, Dang Ho
Milovanović, Milan M.
Zarić, Snežana D.
Article (Accepted Version)
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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 , 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 POBMUPwhich is the iridium 1,3-bis[(di-tert-butylphosphino)oxy]benzene (POCOP) complex isol...ated by Brookhart etal.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.
Keywords:coordination modes / Si ligands / silanes / silicon / transition metals
Source:Chemistry - A European Journal, 2017, 23, 67, 17058-17069
- Wiley-V C H Verlag Gmbh, Weinheim
- Agence Nationale de la Recherche ANR project COCOORDCHEM
- University of Strasbourg
- French Government (via Campus France)
- LABEX Chimie des Systemes Complexes
- This is the peer-reviewed version of the following article: Binh, D. H.; Milovanović, M.; Puertes-Mico, J.; Hamdaoui, M.; Zarić, S. D.; Djukic, J.-P. Is the R 3 Si Moiety in Metal–Silyl Complexes a Z Ligand? An Answer from the Interaction Energy. Chemistry - A European Journal 2017, 23 (67), 17058–17069. https://doi.org/10.1002/chem.201703373
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3056