Electron Distribution, Bonding, andJ(Si−H) NMR Coupling Constant in (η5-C5H5)(CO)2MnHSiCl3:  The Molecular Orbital View

Lichtenberger, Dennis L.

doi:10.1021/om030121i

Cited by 41 publications

(38 citation statements)

References 25 publications

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“…More information could be now gained thanks to recent improvements in DFT calculations, which allow calculations of J SiH values. [34] Generally, a negative value is the sign of a direct Si-H interaction as 1 J SiH are negative due to the negative magnetogyric value of silicon. [35] Decoalescence of the hydride signal in a polyhydride system is rarely observed.…”

Section: Primary Silanesmentioning

confidence: 99%

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

2006

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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)

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Section: Primary Silanesmentioning

confidence: 99%

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

2006

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“…Two sets of 29 Si satellites of the W-H resonance result from the presence of two silicon ligands at the tungsten centre. The 1 J Si-H value of 43 Hz is a typical J Si-H value for g 2 -silane complexes, which usually falls in the range 30-100 Hz [1,[16][17][18][19][20][21][32][33][34], and proves a r (Si-H) interaction with the tungsten centre. The second J Si-H value of 34 Hz establishes the presence of another silicon atom at the tungsten center, coupled with a proton through two bonds.…”

Section: Resultsmentioning

confidence: 91%

Activation of the Si–H bond of Et2SiH2 in photochemical reaction with W(CO)6: Spectroscopic characterization of intermediate W–Si compounds and the revisited crystal structure of the bis{(μ-η2-hydridodiethylsilyl)tetracarbonyltungsten(I)} complex [{W(μ-η2-H–SiEt2)(CO)4}2]

Gądek

Kochel

Szymańska-Buzar

2007

Journal of Organometallic Chemistry

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“…[43] In this work we calculated hydride chemical shifts and the coupling constants between the hydride and silyl ligands for carbonyl complexes [Fe(Cp)(OC)(SiMe n Cl 3Àn )H(X)] (X = H, Me, SiMe n Cl 3Àn ) (n = 0-3; Table 11). …”

Section: à Ligand Frozen In the Midway Of Transformation From The (H)mentioning

confidence: 99%

Unique {H(SiR₃)₂}, (H₂SiR₃), H(HSiR₃), and (H₂)SiR₃Ligand Sets Supported by the {Fe(Cp)(L)} Platform (L=CO, PR₃)

Vyboishchikov

Nikonov

2006

Chemistry A European J

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This work deals with the type and incidence of nonclassical Si--H and H--H interactions in a family of silylhydride complexes [Fe(Cp)(OC)(SiMe(n)Cl(3-n))H(X)] (X=SiMe(n)Cl(3-n), H, Me, n=0-3) and [Fe(Cp)(Me(3)P)(SiMe(n)Cl(3-n))(2)H] (n=0-3). DFT calculations complemented by atom-in-molecule analysis and calculations of NMR hydrogen-silicon coupling constants revealed a surprising diversity of nonclassical Si--H and H--H interligand interactions. The compounds [Fe(Cp)(L)(SiMe(n)Cl(3-n))(2)H] (L=CO, PMe(3); n=0-3) exhibit an unusual distortion from the ideal piano-stool geometry in that the silyl ligands are strongly shifted toward the hydride and there is a strong trend towards flattening of the {FeSi(2)H} fragment. Such a distortion leads to short Si--H contacts (range 2.030-2.075 A) and large Mayer bond orders. A novel feature of these extended Si--H interactions is that they are rather insensitive towards the substitution at the silicon atom and the orientation of the silyl ligand relatively the Fe--H bond. NMR spectroscopy and bonding features of the related complexes [Fe(Cp)(OC)(SiMe(n)Cl(3-n))H(Me)] (n=0-3) allow for their rationalization as usual eta(2)-Si--H silane sigma-complexes. The series of "dihydride" complexes [Fe(Cp)(OC)(SiMe(n)Cl(3-n))H(2)] (n=0-3) is different from the previous two families in that the type of interligand interactions strongly depends on the substitution on silicon. They can be classified either as usual dihydrogen complexes, for example, [Fe(Cp)(OC)(SiMe(2)Cl)(eta(2)-H(2))], or as compounds with nonclassical H--Si interactions, for example, [Fe(Cp)(OC)(H)(2)(SiMe(3))] (16). These nonclassical interligand interactions are characterized by increased negative J(H,Si) (e.g. -27.5 Hz) and increased J(H,H) (e.g. 67.7 Hz).

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Electron Distribution, Bonding, andJ(Si−H) NMR Coupling Constant in (η⁵-C₅H₅)(CO)₂MnHSiCl₃: The Molecular Orbital View

Cited by 41 publications

References 25 publications

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

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

Activation of the Si–H bond of Et2SiH2 in photochemical reaction with W(CO)6: Spectroscopic characterization of intermediate W–Si compounds and the revisited crystal structure of the bis{(μ-η2-hydridodiethylsilyl)tetracarbonyltungsten(I)} complex [{W(μ-η2-H–SiEt2)(CO)4}2]

Unique {H(SiR₃)₂}, (H₂SiR₃), H(HSiR₃), and (H₂)SiR₃Ligand Sets Supported by the {Fe(Cp)(L)} Platform (L=CO, PR₃)

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Electron Distribution, Bonding, andJ(Si−H) NMR Coupling Constant in (η5-C5H5)(CO)2MnHSiCl3: The Molecular Orbital View

Cited by 41 publications

References 25 publications

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

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

Activation of the Si–H bond of Et2SiH2 in photochemical reaction with W(CO)6: Spectroscopic characterization of intermediate W–Si compounds and the revisited crystal structure of the bis{(μ-η2-hydridodiethylsilyl)tetracarbonyltungsten(I)} complex [{W(μ-η2-H–SiEt2)(CO)4}2]

Unique {H(SiR3)2}, (H2SiR3), H(HSiR3), and (H2)SiR3Ligand Sets Supported by the {Fe(Cp)(L)} Platform (L=CO, PR3)

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Electron Distribution, Bonding, andJ(Si−H) NMR Coupling Constant in (η⁵-C₅H₅)(CO)₂MnHSiCl₃: The Molecular Orbital View

Unique {H(SiR₃)₂}, (H₂SiR₃), H(HSiR₃), and (H₂)SiR₃Ligand Sets Supported by the {Fe(Cp)(L)} Platform (L=CO, PR₃)