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Issue 18, 2019
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Controllable access to P-functional [3]ferrocenophane and [4]ferrocenophane frameworks

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Abstract

Condensation of secondary 1,1′-diaminoferrocenes with phosphorus trihalides (PCl3 or PBr3) yielded either P-halo-1,3-diaza-2-phospha[3]ferrocenophanes or 1,1′-diaminoferrocenediyl-bis(dichlorophosphines), respectively. The latter provide controlled access to both [3]- and [4]ferrocene frameworks. Thus, reductive coupling with magnesium gave diaza-diphospha[4]ferrocenophane-annelated tetraphosphetanes, while a reaction with LiNMe2 produced a P-chloro-diazaphospha[3]ferrocenophane. Condensation of diaminoferrocenes and aminodichlorophosphines were mostly unselective, but afforded in one case a 3-amino[3]ferrocenophane. All reaction products were characterised by spectroscopic and single-crystal XRD studies. DFT studies indicate that the product selectivity in the reactions studied depends on a combination of kinetic and thermodynamic effects, which correlate subtly with the steric bulk of the N-substituents. Cyclic voltammetry measurements revealed that the ferrocenophanes can undergo multiple oxidation events, the first of which may according to DFT studies be located in both the ferrocene and aminophosphine units. The quantum chemical studies provided also insight into stereochemical aspects like ring strain in the ferrocenophane units.

Graphical abstract: Controllable access to P-functional [3]ferrocenophane and [4]ferrocenophane frameworks

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Publication details

The article was received on 27 Feb 2019, accepted on 04 Apr 2019 and first published on 04 Apr 2019


Article type: Paper
DOI: 10.1039/C9DT00892F
Dalton Trans., 2019,48, 6236-6247

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    Controllable access to P-functional [3]ferrocenophane and [4]ferrocenophane frameworks

    S. Weller, S. H. Schlindwein, C. M. Feil, Z. Kelemen, D. Buzsáki, L. Nyulászi, S. Isenberg, R. Pietschnig, M. Nieger and D. Gudat, Dalton Trans., 2019, 48, 6236
    DOI: 10.1039/C9DT00892F

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