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

Stefan Weller; Simon H. Schlindwein; Christoph M. Feil; Zsolt Kelemen; Dániel Buzsáki; László Nyulászi; Stefan Isenberg; Rudolf Pietschnig; Martin Nieger; Dietrich Gudat

doi:10.1039/C9DT00892F

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

Stefan Weller,^a Simon H. Schlindwein,^a Christoph M. Feil,^a Zsolt Kelemen,

‡^b Dániel Buzsáki,

^b László Nyulászi,

*^b Stefan Isenberg,^c Rudolf Pietschnig,

*^c Martin Nieger

^d and Dietrich Gudat

*^a

Author affiliations

* Corresponding authors

^a Institut für Anorganische Chemie, University of Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart, Germany
E-mail: gudat@iac.uni-stuttgart.de

^b Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, and MTA-BME Computation Driven Chemistry Research Group, Szent Gellért tér 4, 1111 Budapest, Hungary

^c Institut für Chemie und CINSaT, Universität Kassel, Heinrich Plett-Straße 40, 34132 Kassel, Germany

^d Department of Chemistry, University of Helsinki, P.O Box 55, 00014 University of Helsinki, Finland

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.

Dalton Transactions

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

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