Synthesis and reactivity of the imidotungsten methyl cation [W(N2Npy)(NPh)Me]+: CO2 adds to the W=NPh bond and does not insert into the W-Me bond

Benjamin D. Ward; Eric Clot; Stuart R. Dubberley; Lutz H. Gade; Philip Mountford

doi:10.1039/b208327b

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Synthesis and reactivity of the imidotungsten methyl cation [W(N<sub>2</sub>Npy)(NPh)Me]<sup>+</sup>: CO<sub>2</sub> adds to the W=NPh bond and does not insert into the W-Me bond

Journal article

Peer reviewed

Synthesis and reactivity of the imidotungsten methyl cation [W(N₂Npy)(NPh)Me]⁺: CO₂ adds to the W=NPh bond and does not insert into the W-Me bond

Benjamin D. Ward, Eric Clot, Stuart R. Dubberley, Lutz H. Gade and Philip Mountford

Chemical Communications, pp.2618-2619

21/11/2002

DOI: https://doi.org/10.1039/b208327b

Abstract

CATALYSTS

LIGANDS

ALKYL

ACTIVATION

METATHESIS POLYMERIZATION

ETHYLENE POLYMERIZATION

TRANSITION-METALS

CARBON-DIOXIDE

COMPLEXES

IMIDO

The imidotungsten dimethyl compound [W(N2Npy)(NPh)Me-2] 2 reacts with BAr3F to form the cationic complex [W(N2Npy)(NPh)Me](+) 3(+) [anion = [Me-BAr3F]-; Ar-F C6F5; N2Npy MeC(2-C5H4N)(CH2NSiMe3)(2)] which undergoes methyl group exchange with added 2, [Cp2ZrMe2] or ZnMe2; treatment of cation 3(+) with CO2 or isocyanates leads to cycloaddition reactions at the W=NPh bond and not insertion into the W-Me bond, despite the latter product being the most thermodynamically favourable according to DFT calculations.

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Title: Synthesis and reactivity of the imidotungsten methyl cation [W(N₂Npy)(NPh)Me]⁺: CO₂ adds to the W=NPh bond and does not insert into the W-Me bond
Creators - without role: Benjamin D. Ward - University of Oxford
Eric Clot - Université de Montpellier
Stuart R. Dubberley - University of Oxford
Lutz H. Gade - Institut de Chimie
Philip Mountford - University of Oxford
Publication Details: Chemical Communications, pp.2618-2619
Identifiers: 9944978409311
Academic Unit: Université de Montpellier
Language: English
Resource Type: Journal article
Local Fields: hal-00429097