<i>J</i>(Si,H)‐Kopplungskonstanten in nicht‐klassischen Übergangsmetallsilankomplexen

Scherer, Wolfgang; Meixner, Petra; Batke, Kilian; Barquera‐Lozada, José Enrique; Ruhland, Klaus; Fischer, Andreas; Eickerling, Georg; Eichele, Klaus

doi:10.1002/ange.201604001

Cited by 3 publications

(2 citation statements)

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“…In summary, the complex electronic situation of the metal‐“bound” silane has indeed fueled a range of reports that dealt with the electronic relationships within the M(H)(SiR 3 ) unit, with some authors considering that any metal–silane adduct in which some Si−H interaction persists should be considered to be an “arrested intermediate” of an aborted ideal oxidative addition . The historical Chalk–Harrod mechanism considers the initial reaction of a silane of the general formula R 3 SiH (R=aryl, alkyl, halido, and hydrogen) with a metal centre to be oxidative addition, thus leading logically to the formal oxidation of the metal centre and the creation of two new M−H and M−SiR 3 bonds; furthermore, the latter ligands are considered to be of the X‐type according to the covalent‐bond classification (CBC) formalism…”

Section: Introductionmentioning

confidence: 99%

Is the R₃Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

Binh

Milovanović

Puertes-Mico

et al. 2017

Chemistry A European J

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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 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 SiR groups to behave chemically as metal-bound "silylium" ions, namely, [SiR ] . 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 SiEt group that is weakly bonded to the hydrido-iridium motif.

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Section: Introductionmentioning

confidence: 99%

Is the R₃Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

Binh

Milovanović

Puertes-Mico

et al. 2017

Chemistry A European J

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“…Anhand der chemischen Verschiebung und der Änderungen der Kopplungskonstanten lassen sich grundsätzlich Aussagen über die Änderung der Bindungsstärke treffen. [91] fert. [92] Abgesehen vom genauen Betrachten der elektronischen Struktur im Sinne der Molekülorbitaltheorie, lassen sich auch darüber hinaus durch die Untersuchung der Ladungsdichteverteilung wichtige Erkenntnisse über die Bindungssituation erhalten.…”

Section: Wechselwirkungunclassified

Experimentelle Ladungsdichteuntersuchungen von nichtkovalenten Wechselwirkungen

Helena¹

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Si–H···Se Chalcogen–Hydride Bond Quantified by Diffraction and Topological Analyses

et al. 2022

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The Si−H•••Se contact in 1-mesitylselanyl-8-(dimethylsilyl)naphthalene (1), which exhibits the spatial arrangement of a δ-agostic interaction from geometric considerations, was investigated. Is this just enforced by close 1,8-proximity or is this a favorable interaction? Charge density studies are best suited to investigate the exact origin of the interaction and to quantify the properties. Hence, they are most elucidating. Highresolution X-ray diffraction data of 1 were collected, and a multipole refinement followed by a topological analysis using Bader's quantum theory of atoms in molecules was employed. The resulting bond properties were set in relation to high-level computational parameters. The comparison to Si−H•••[M] agostics, hydride bonding, chalcogen bonds, and chargeinverted hydrogen bonds qualified the Si−H•••Se noncovalent interaction to be best classified as a chalcogen−hydride bond.

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J(Si,H)‐Kopplungskonstanten in nicht‐klassischen Übergangsmetallsilankomplexen

Cited by 3 publications

References 35 publications

Is the R₃Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

Is the R₃Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

Experimentelle Ladungsdichteuntersuchungen von nichtkovalenten Wechselwirkungen

Si–H···Se Chalcogen–Hydride Bond Quantified by Diffraction and Topological Analyses

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J(Si,H)‐Kopplungskonstanten in nicht‐klassischen Übergangsmetallsilankomplexen

Cited by 3 publications

References 35 publications

Is the R3Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

Is the R3Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

Experimentelle Ladungsdichteuntersuchungen von nichtkovalenten Wechselwirkungen

Si–H···Se Chalcogen–Hydride Bond Quantified by Diffraction and Topological Analyses

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Is the R₃Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

Is the R₃Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy