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Synthesis and Reactivity of a Neutral Homocyclic Silylene.

ABSTRACT: Isolation of the neutral homocyclic silylene 2 is possible via amine ligand abstraction with potassium graphite (KC₈ ) and subsequent reaction with SiMe₃ Cl from a bicyclic silicon(I) amide J. This reaction proceeds via an anionic homoaromatic silicon ring compound 1 as an intermediate. The twofold-coordinated silicon atom in the homocyclic silylene 2 is stabilized by an allyl-type π-electron delocalization. 2 reacts in an oxidative addition with two equivalents of MeOH and in cycloadditions with ethene, phenylacetylene, diphenylacetylene and with 2,3-dimethyl-1,3-butadiene to afford novel functionalized ring compounds.

SUBMITTER: Keuter J

PROVIDER: S-EPMC9299817 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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Synthesis and Reactivity of a Neutral Homocyclic Silylene.

Keuter Jan J Hepp Alexander A Massolle Anja A Neugebauer Johannes J Mück-Lichtenfeld Christian C Lips Felicitas F

Angewandte Chemie (International ed. in English) 20211214 5

Isolation of the neutral homocyclic silylene 2 is possible via amine ligand abstraction with potassium graphite (KC<sub>8</sub> ) and subsequent reaction with SiMe<sub>3</sub> Cl from a bicyclic silicon(I) amide J. This reaction proceeds via an anionic homoaromatic silicon ring compound 1 as an intermediate. The twofold-coordinated silicon atom in the homocyclic silylene 2 is stabilized by an allyl-type π-electron delocalization. 2 reacts in an oxidative addition with two equivalents of MeOH and ...[more]

PMID: 34797603

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Project description:Manganese disilyl hydride complexes [(dmpe)2MnH(SiH2R)2] (4Ph : R = Ph, 4Bu : R = n Bu) reacted with ethylene to form silene hydride complexes [(dmpe)2MnH(RHSi[double bond, length as m-dash]CHMe)] (6Ph,H : R = Ph, 6Bu,H : R = n Bu). Compounds 6R,H reacted with a second equivalent of ethylene to generate [(dmpe)2MnH(REtSi[double bond, length as m-dash]CHMe)] (6Ph,Et : R = Ph, 6Bu,Et : R = n Bu), resulting from apparent ethylene insertion into the silene Si-H bond. Furthermore, in the absence of ethylene, silene complex 6Bu,H slowly isomerized to the silylene hydride complex [(dmpe)2MnH([double bond, length as m-dash]SiEt n Bu)] (3Bu,Et ). Reactions of 4R with ethylene likely proceed via low-coordinate silyl {[(dmpe)2Mn(SiH2R)] (2Ph : R = Ph, 2Bu : R = n Bu)} or silylene hydride {[(dmpe)2MnH([double bond, length as m-dash]SiHR)] (3Ph,H : R = Ph, 3Bu,H : R = n Bu)} intermediates accessed from 4R by H3SiR elimination. DFT calculations and high temperature NMR spectra support the accessibility of these intermediates, and reactions of 4R with isonitriles or N-heterocyclic carbenes yielded the silyl isonitrile complexes [(dmpe)2Mn(SiH2R)(CNR')] (7a-d: R = Ph or n Bu; R' = o-xylyl or t Bu), and NHC-stabilized silylene hydride complexes [(dmpe)2MnH{[double bond, length as m-dash]SiHR(NHC)}] (8a-d: R = Ph or n Bu; NHC = 1,3-diisopropylimidazolin-2-ylidene or 1,3,4,5-tetramethyl-4-imidazolin-2-ylidene), respectively, all of which were crystallographically characterized. Silyl, silylene and silene complexes in this work were accessed via reactions of [(dmpe)2MnH(C2H4)] (1) with hydrosilanes, in some cases followed by ethylene. Therefore, ethylene (C2H4 and C2D4) hydrosilylation was investigated using [(dmpe)2MnH(C2H4)] (1) as a pre-catalyst, resulting in stepwise conversion of primary to secondary to tertiary hydrosilanes. Various catalytically active manganese-containing species were observed during catalysis, including silylene and silene complexes, and a catalytic cycle is proposed.

Dataset Information

Synthesis and Reactivity of a Neutral Homocyclic Silylene.

Publications

Synthesis and Reactivity of a Neutral Homocyclic Silylene.

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