Chemistry of 2,3-dihydro-2-metallaphenalenes. Part 1. Synthesis of CHRSiMe2CHR′C10H6 (R = R′ = H; R = R′ = SiMe3; And R,R′ = H,SiMe3) and formation of the compound: [{Li(Me2NCH2CH2NMe2)} 2{CHRSiMe2C(SiMe3)C10H6 via Decomposition of [{Li(Me2NCH2CH2NMe2)} 2{1,8-(CHSiMe3)2C10H6}]; Crystal structures of two polymorphs of the silicon heterocycle dilithium complex

Lutz M. Engelhardt, Rocco I. Papasergio, Colin L. Raston, Allan H. White

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The complexes [{Li(tmen)}2{1,8-(CHSiMe3)2C10H 6}] (9) (tmen = NNN′N′-tetramethylethylenediamine) and [{Li(tmen)}{CHSiMe2CH2C10H6}] (13) have been prepared via metallation of species formed by in situ Grignard trapping reactions of 1,8-(ClCH2)2C10H6 with SiMe3Cl and SiMe2Cl2 respectively; synthesis of the siline, meso-CH(SiMe3)SiMe2CH(SiMe3)C 10H6 from (9) is also described. In hexane, (9) decomposes to [{Li(tmen)}2{CHSiMe2C(SiMe3)C 10H6 (10) to yield the compound CH2SiMe2CH(SiMe3)C10H6 on the addition of aqueous HCl, the same product as that obtained from a reaction of (13) with SiMe3Cl. The nature of (10) has been established by X-ray structure determination of two polymorphs, α and β, which differ both in the mode of interaction of the Li(tmen)+ moieties with the carbanion [η63 (α), cf. η43 (β)] and the conformation of the heterocyclic ring.

Original languageEnglish
Pages (from-to)311-320
Number of pages10
JournalJournal of the Chemical Society, Dalton Transactions
Issue number3
DOIs
Publication statusPublished - Mar 1984
Externally publishedYes

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