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Alkali metal derivatives of an ortho-phenylene diamine

Robinson, Sarah; Davies, E. Stephen; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

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Sarah Robinson

E. Stephen Davies

William Lewis

Alexander J. Blake

Stephen T. Liddle


Treatment of the ortho-phenylene diamine C6H4-1,2-{N(H)Tripp}2 (1, PDAH2, Tripp = 2,4,6-triisopropylphenyl) with two equivalents of MR (M = Li, R = Bun; M = Na or K, R = CH2C6H5) afforded the dimetallated alkali metal ortho-phenylene diamide dianion complexes [(PDALi2)(THF)3] (2), [{(PDANa2)(THF)2}2] (3), and [{(PDAK2)(THF)3}2] (4). In contrast, treatment of 2 with two equivalents of rubidium or cesium 2-ethylhexoxide, or treatment of 1 with two equivalents of MR (M = Rb or Cs, R = CH2C6H5) did not afford the anticipated dialkali metal ortho-phenylene diamide dianion derivatives and instead formally afforded the monometallic ortho-diiminosemiquinonate radical anion species [PDAM] (M = Rb, 5; M = Cs, 6). The structure of 2 is monomeric with one lithium coordinated to the two nitrogen centres and the other lithium η4-coordinated to the diazabutadiene portion of the PDA scaffold. Similar structural cores are observed for 3 and 4, except that the larger sodium and potassium ions give dimeric structures linked by multi-hapto interactions from the PDA backbone phenyl ring to an alkali metal centre. Complex 5 was not characterised in the solid state, but the structure of 6 reveals coordination of cesium ions to both PDA amide centres and multi-hapto interactions to a PDA backbone phenyl ring in the next unit to generate a one-dimensional polymer. Complexes 2–6 have been variously characterised by X-ray crystallography, multi-nuclear NMR, FTIR, and EPR spectroscopies, and CHN microanalyses.


Robinson, S., Davies, E. S., Lewis, W., Blake, A. J., & Liddle, S. T. (2013). Alkali metal derivatives of an ortho-phenylene diamine. Dalton Transactions, 43(11),

Journal Article Type Article
Acceptance Date Oct 29, 2013
Publication Date Oct 31, 2013
Deposit Date Sep 27, 2017
Publicly Available Date Sep 27, 2017
Journal Dalton Transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 43
Issue 11
Public URL
Publisher URL!divAbstract


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