Persistent π-arene interactions in bulky formamidinate complexes of potassium

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2007

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Cole, M.
Davies, A.
Jones, C.
Junk, P.

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Journal article

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Journal of Organometallic Chemistry, 2007; 692(12):2508-2518

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Marcus L. Cole, Aaron J. Davies, Cameron Jones, Peter C. Junk

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Abstract

The reaction of potassium hexamethyldisilazide (K-HMDS) with 1 equiv. of the bulky formamidine N(Diep){double bond, long}C(H)NH(Diep) (DiepFormH, Diep = 2,6-Et<inf>2</inf>C<inf>6</inf>H<inf>3</inf>) in THF yields the half deprotonated compound [K(DiepForm)(DiepFormH)] (1), which exhibits suppressed reactivity with the hexamethyldisilazide anion. Reaction of 1 with n-BuLi gives the polymer [{Li(THF)<inf>2</inf>K(DiepForm)<inf>2</inf>}<inf>n</inf>] (2). Preparation of 1 in the presence of the chelating solvents 1,2-dimethoxyethane (DME) or N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) gives the fully deprotonated species [{K<inf>3</inf>(DiepForm)<inf>3</inf>(DME)<inf>3</inf>}<inf>n</inf>] (3) and [{K(PMDETA)K(DiepForm)<inf>2</inf>}<inf>n</inf>] (6). The syntheses of compounds 1-3, 6 and related compounds, e.g. [{K<inf>3</inf>{N(Dimp)C(H)N(Dimp)}<inf>3</inf>(DME)<inf>3</inf>}<inf>n</inf>] (4) (Dimp = 2,6-Me<inf>2</inf>C<inf>6</inf>H<inf>3</inf>), are described. © 2007 Elsevier B.V. All rights reserved.

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Copyright © 2007 Elsevier B.V. All rights reserved.

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