Deviation from the ideal octahedral field vs. alkyl distortion in d0 metal-alkyl complexes: a MO study

Demolliens, A.; Jean, Y. C.; Eisenstein, Odile

doi:10.1021/om00138a027

Cited by 67 publications

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“…It was also found that a major component of the stabilization derives from reorganization of the MÀC bond. Direct CÀH donation to the metal plays a minor role according to this study, a finding contrasting with that of a similar EHMO study of the b-agostic model system [EtTiH 5 ] 2À (39), [78] which supported a significant M···HC interaction, as described by Brookhart and Green in terms of a 3c-2e covalent M···HC interaction.…”

Section: Theoretical Treatment Of the Agostic Interactioncontrasting

confidence: 99%

Agostic Interactions in d⁰Metal Alkyl Complexes

2004

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The phenomenon of agostic interactions is reviewed and the nature of the interaction is revisited. A historical perspective is followed by an overview of experimental techniques used to diagnose agostic behavior, and previous interpretations of agostic bonding are presented. A series of simple metal alkyl complexes is considered and a new model for the phenomenon in d(0) systems is developed which sets them apart from agostic late-transition-metal complexes. Factors such as the valence electron count and coordination number of the metal center are revealed to be unimportant in facilitating the interaction in most d(0) systems. The charge density distribution in several transition-metal alkyl complexes is explored by experimental and theoretical techniques, including the powerful "Atoms in Molecules" approach. Local charge concentrations are shown to play an important role in the agostic interaction. Finally, we demonstrate for the first time a way to manipulate and control the magnitude and disposition of such local charge concentrations, and hence the strength of agostic interactions in d(0) metal alkyl complexes.

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Section: Theoretical Treatment Of the Agostic Interactioncontrasting

confidence: 99%

Agostic Interactions in d⁰Metal Alkyl Complexes

2004

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“…After its synthesis, the structure was established in 1996 by Seppelt [5], [6,7] and Kaupp [8]. The geometry was calculated by Demolliens et al [9] and Kang et al [10]. However, until 2015 and to our knowledge there was no report on the catalytic activity of this homoleptic complex.…”

Section: Introductionmentioning

confidence: 99%

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

Dey

Samantaray

Callens

et al. 2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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-Tungsten-hexa-methyl readily reacts with B(C 6 F 5 ) 3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1 H NMR, 13 C NMR, 1 H-13 C NMR correlation spectroscopy. Unlike WMe 6 , this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe 6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene. C RMN, 1 H-13 C RMN. À la différence du WMe 6 , ce complexe cationique a une barrière énergétique faible pour former un intermédiaire de carbène tungstène, ce qui a été ultérieurement étayé par le fait que le WMe 6 seul n'a pas d'activité dans la réaction de métathèse des oléfines, tandis que le complexe cationique montre une activité catalytique pour l'autométathèse d'1-octène.

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“…[14] Since the pioneering studies by Eisenstein et al, [15] which predicted a non- predicted by theoretical studies. [14,19] Several models based on MO theory have been advanced to rationalize this phenomenon, [14,19] but these cannot compete with the simplicity and success rate of the VSEPR model in predicting the geometries of main group molecules.…”

Section: Introductionmentioning

confidence: 99%

Valence Shell Charge Concentrations at Pentacoordinate d⁰Transition‐Metal Centers: Non‐VSEPR Structures of Me₂NbCl₃and Me₃NbCl₂

McGrady

Haaland

Verne

et al. 2005

Chemistry A European J

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The molecular structures of the monomeric, pentacoordinated methylchloroniobium(V) compounds Me 3 NbCl 2 and Me 2 NbCl 3 have been determined by gas electron diffraction (GED) and Density Functional Theory (DFT) calculations, and, for Me 3 NbCl 2 , by single crystal X-ray diffraction. Each of the molecules is found to have a heavy-atom skeleton in the form of a trigonal bipyramid (TBP) with Cl atoms in the axial positions, in accord with their vibrational spectra. The TBP is somewhat distorted in the case of Me 2 NbCl 3 with the two axial Nb-Cl bonds bent away from the equatorial, slightly shorter Nb-Cl bond. In the case of Me 3 NbCl 2 , moreover, the X-ray model suggests structural distortions away from the idealized C 3h geometry, in line with the results of quantum

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Deviation from the ideal octahedral field vs. alkyl distortion in d0 metal-alkyl complexes: a MO study

Cited by 67 publications

References 0 publications

Agostic Interactions in d⁰Metal Alkyl Complexes

Agostic Interactions in d⁰Metal Alkyl Complexes

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

Valence Shell Charge Concentrations at Pentacoordinate d⁰Transition‐Metal Centers: Non‐VSEPR Structures of Me₂NbCl₃and Me₃NbCl₂

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Deviation from the ideal octahedral field vs. alkyl distortion in d0 metal-alkyl complexes: a MO study

Cited by 67 publications

References 0 publications

Agostic Interactions in d0Metal Alkyl Complexes

Agostic Interactions in d0Metal Alkyl Complexes

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

Valence Shell Charge Concentrations at Pentacoordinate d0Transition‐Metal Centers: Non‐VSEPR Structures of Me2NbCl3and Me3NbCl2

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Agostic Interactions in d⁰Metal Alkyl Complexes

Agostic Interactions in d⁰Metal Alkyl Complexes

Valence Shell Charge Concentrations at Pentacoordinate d⁰Transition‐Metal Centers: Non‐VSEPR Structures of Me₂NbCl₃and Me₃NbCl₂