Synthesis and crystal structures of [C6H4SC(-..S)-..NNa·3P(NMe2) 3O·NaN-..(S-..)CSC6H4] and [C6H4SC(-..S)-..NLi·pmdien] (pmdien = N,N,N′,N″,N″-pentamethyldiethylenetriamine): Alkali-metal amides from 2-sulfanylbenzothiazole

Philip C. Andrews, George A. Koutsantonis, Colin L. Raston

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Abstract

Reaction of 2-sulfanylbenzothiazole with MBun (M = Li or Na) in the presence of the Lewis-base donors Me2NCH2CH2NMeCH2CH 2NMe2 (pmdien) and P(NMe2)3O gave, respectively, the monomer [C6H4SC(-..S)-..NLi·pmdien] and the dimer [C4H4SC(-..S)-..NNa·3P(NMe2) 3O·NaNA-.. (S-..CSC6H4], the structures of which have been determined by X-ray crystallography. In common with other structurally characterised sulfanylbenzothiazolate complexes, both the five-co-ordinate metal cations are involved in bridged bonding with the exocyclic S and the amido N. The amido N+-M- is the formal bond making these two structures amide rather than thiolate complexes. In the sodium complex this is clear [N-Na 2.46(1) Å], however, in the lithium case the Li-N bond is exceptionally long [amido N-Li 2.14(1) Å], but an analysis of the bond lengths within the sulfanylbenzothiazolate moiety verifies its amido nature. The two complexes also show rare secondary bonding of the exocyclic S atoms by the alkali-metal cations, exo-S-Li 2.73(1) and exo-S-Na 2.995(1) and 2.951(7) Å.

Original languageEnglish
Pages (from-to)4059-4065
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number24
DOIs
Publication statusPublished - 1 Dec 1995

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