Preparation and Structures of [W(CH3)6], [Re(CH3)6], [Nb(CH3)6], and [Ta(CH3)6]

Kleinhenz, Sven; Pfennig, Valérie; Seppelt, Konrad

doi:10.1002/(sici)1521-3765(19980904)4:9<1687::aid-chem1687>3.3.co;2-i

Cited by 27 publications

(79 citation statements)

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“…One early example of methyl complex of group 6 metals is homoleptic WMe6, which was synthesized by Wilkinson in 1973, 8 however its distorted trigonal prismatic (C3v symmetry) solid state structure had to wait over 30 years to be revealed by Seppelt et al 52 The same group has contributed with many examples of homoleptic methyl complexes of groups 5 to 7. [53][54][55] Most methyl complexes of group 6 metals reported recently are chromium complexes. Mono Cp-Cr species have been used as commercial ethylene polymerization catalysts.…”

Section: General Methods For the Generation Of Tm-ch3 Bonds In Transimentioning

confidence: 99%

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Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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Section: General Methods For the Generation Of Tm-ch3 Bonds In Transimentioning

confidence: 99%

“…More abundant are the complexes with Re-CH3 bonds. 54,55 Many recent examples are structurally derived from Re(VIII) oxides. One relevant example is methyltrioxorhenium (MTO), which is a versatile catalyst in oxidation and hydrogen transfer reactions including olefin epoxidation.…”

Section: Groupmentioning

confidence: 99%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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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].…”

Section: Introductionmentioning

confidence: 93%

“…The molecular precursor WMe 6 was prepared from WCl 6 and (CH 3 ) 2 Zn, following the literature procedure [1,6]. To a mixture of WCl 6 (1.80 g, 4.5 mmol) in dichloromethane (25 mL) was added (CH 3 ) 2 Zn (13.6 mmol, 1.0 M in heptane) at À80°C, and after addition, the reaction mixture was warmed to À35°C and stirred at this temperature for another 30 min.…”

Section: Preparation Of Hexamethyltungsten Wmementioning

confidence: 99%

“…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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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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A Continuous Chirality Analysis of Homoleptic Hexacoordinated Complexes

Álvarez

Pinsky

Avnir

2001

Eur. J. Inorg. Chem.

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Hexacoordinated complexes are generally considered to be potentially chiral if they have either at least two bidentate ligands or at least three different monodentate ligands. Here we draw attention to a neglected general possibility, namely that homoleptic hexacoordinated complexes with molecular structures in between octahedral and trigonal prismatic, following the Bailar twisting route, are chiral. A quantitative evaluation of the degree of chirality of such hexakis(mondentate) complexes shows that they reach maximum chirality when the trigonal rotation angle of the prism reaches 23°. Model calculations and analysis of experimental X‐ray structures are in good agreement. The most chiral of the complexes with monodentate ligands that have been analyzed is [Zr(SC6H4‐4‐OMe)6]2−. The validity of the theoretical prediction is also corroborated by an analysis of the chirality of the coordination sphere in twisted tris(chelate) complexes.

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Preparation and Structures of [W(CH3)6], [Re(CH3)6], [Nb(CH3)6], and [Ta(CH3)6]

Cited by 27 publications

References 0 publications

Methyl Complexes of the Transition Metals

Methyl Complexes of the Transition Metals

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

A Continuous Chirality Analysis of Homoleptic Hexacoordinated Complexes

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