Is the R3Si Moiety in Metal-Silyl Complexes a Z ligand? AnAnswer from the Interaction Energy
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2017
Authors
Binh, Dang HoMilovanović, Milan M.

Puertes-Mico, Julia
Hamdaoui, Mustapha

Zarić, Snežana D.

Đukić, Jean-Pierre

Article (Published 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 metalsSource:
Chemistry. A European Journal, 2017, 23, 67, 17058-17069Publisher:
- Wiley-V C H Verlag Gmbh, Weinheim
Funding / projects:
- Agence Nationale de la Recherche ANR project COCOORDCHEM
- ANR
- University of Strasbourg
- French Government (via Campus France)
- LABEX Chimie des Systemes Complexes
- CNRS
Note:
- Peer-reviewed manuscript: http://cherry.chem.bg.ac.rs/handle/123456789/3054
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3056
DOI: 10.1002/chem.201703373
ISSN: 0947-6539
PubMed: 28877385
WoS: 000418570000021
Scopus: 2-s2.0-85034102741
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Hemijski fakultetTY - JOUR AU - Binh, Dang Ho AU - Milovanović, Milan M. AU - Puertes-Mico, Julia AU - Hamdaoui, Mustapha AU - Zarić, Snežana D. AU - Đukić, Jean-Pierre PY - 2017 UR - https://cherry.chem.bg.ac.rs/handle/123456789/2571 AB - 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 isolated 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. PB - Wiley-V C H Verlag Gmbh, Weinheim T2 - Chemistry. A European Journal T1 - Is the R3Si Moiety in Metal-Silyl Complexes a Z ligand? AnAnswer from the Interaction Energy VL - 23 IS - 67 SP - 17058 EP - 17069 DO - 10.1002/chem.201703373 UR - Kon_3387 ER -
@article{ author = "Binh, Dang Ho and Milovanović, Milan M. and Puertes-Mico, Julia and Hamdaoui, Mustapha and Zarić, Snežana D. and Đukić, Jean-Pierre", year = "2017", 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 , 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 isolated 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.", publisher = "Wiley-V C H Verlag Gmbh, Weinheim", journal = "Chemistry. A European Journal", title = "Is the R3Si Moiety in Metal-Silyl Complexes a Z ligand? AnAnswer from the Interaction Energy", volume = "23", number = "67", pages = "17058-17069", doi = "10.1002/chem.201703373", url = "Kon_3387" }
Binh, D. H., Milovanović, M. M., Puertes-Mico, J., Hamdaoui, M., Zarić, S. D.,& Đukić, J.. (2017). Is the R3Si Moiety in Metal-Silyl Complexes a Z ligand? AnAnswer from the Interaction Energy. in Chemistry. A European Journal Wiley-V C H Verlag Gmbh, Weinheim., 23(67), 17058-17069. https://doi.org/10.1002/chem.201703373 Kon_3387
Binh DH, Milovanović MM, Puertes-Mico J, Hamdaoui M, Zarić SD, Đukić J. Is the R3Si Moiety in Metal-Silyl Complexes a Z ligand? AnAnswer from the Interaction Energy. in Chemistry. A European Journal. 2017;23(67):17058-17069. doi:10.1002/chem.201703373 Kon_3387 .
Binh, Dang Ho, Milovanović, Milan M., Puertes-Mico, Julia, Hamdaoui, Mustapha, Zarić, Snežana D., Đukić, Jean-Pierre, "Is the R3Si Moiety in Metal-Silyl Complexes a Z ligand? AnAnswer from the Interaction Energy" in Chemistry. A European Journal, 23, no. 67 (2017):17058-17069, https://doi.org/10.1002/chem.201703373 ., Kon_3387 .