Bis-[3]Ferrocenophanes with Central >E-E'< Bonds (E, E'=P, SiH): Preparation, Properties, and Thermal Activation.

Stefan Isenberg,Dietrich Gudat,Brigitte Schwederski,Srećko Valić,Rudolf Pietschnig,Stefan Weller,Christoph M Feil,Zsolt Kelemen,Martin Nieger,László Nyulászi,Clemens Bruhn,Kristijan Krekić,Martin Maurer,Denis Kargin

doi:10.1002/open.201900182

Abstract

A series of bis‐[3]ferrocenophanes of the general type Fe(C5H4E’)2E−E(E'C5H4)2Fe (E=P, SiH and E’=PtBu, NneoPentyl, NSi(CH3)3) with an isolobal molecular framework have been prepared and characterized by heteronuclear NMR spectroscopy and X‐ray crystallography. The thermal dissociation behavior with respect to homolytic fission of the central bond generating phosphorus centered radicals was investigated using EPR spectroscopy and quantum chemical calculations.

Highlights

(CH3)3) with an isolobal molecular framework have been prepared and characterized by heteronuclear NMR spectroscopy and X-ray crystallography
We have shown that formally linking two terminal phosphorus atoms by a ferrocene fragment can provide a suitable template for the assembly of such cyclic structures.[3]
Organopolyphosphorus frameworks may be regarded as molecular models for sections of phosphorus modifications such as the (> P)2P P(P

Summary

Full Papers

Bis-[3]Ferrocenophanes with Central > E E’ < Bonds (E, E’=P, SiH): Preparation, Properties, and Thermal Activation. Zsolt Kelemen,[a, d] Clemens Bruhn,[a] Kristijan Krekić,[a] Martin Maurer,[a] Christoph M. Beyond its beneficial structural features, the ferrocene unit usually provides reversible redox activity, where oxidation at iron may entail electron transfer with the phosphorus atoms.[5] Such oxidized systems could be related to cationic polyphosphorus compounds as described by Weigand and Burford et al.[6] Phosphorus modifications such as black phosphorus and especially its exfoliated version, phosphorene, attracted substantial interest because of their unique electronic and thermoelectric material properties.[1] While in most crystalline phosphorus modifications the relative orientation of the phosphorus lone-pairs is constrained by the three-dimensional lattice, molecular organopolyphosphorus frameworks can give rise to rather complex mixtures of diastereomers.

Results and Discussion

Conclusions

Conflict of Interest