Stereochemical Alignment in Triphospha[3]ferrocenophanes

Stefan Borucki, Zsolt Kelemen, Martin Maurer, Clemens Bruhn, L. Nyulászi, Rudolf Pietschnig

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A series of triphospha[3]ferrocenophanes of the type Fe(C5H4-PtBu)2PX with X=H, F, Cl, Br, I, NEt2, tBu has been prepared and characterized by heteronuclear NMR spectroscopy and X-ray crystallography. Despite having three stereogenic centers, the selective formation of a reduced number of diastereomers (either one or two) has been observed for these ferrocenophanes. Theoretical calculations revealed that the inversion of the central stereogenic center inverts the frontier orbital sequence leading to either an iron or a phosphorus centered HOMO depending on the respective diastereomer. CV measurements supported these results. For the all-tert-butyl substituted [3]ferrocenophane Fe(C5H4)2(PtBu)3 a chiral staggered conformation has been found in the solid state which differs substantially from the only other all-organo substituted [3]ferrocenophane, Fe(C5H4)2(PPh)3.

Original languageEnglish
Pages (from-to)10438-10450
Number of pages13
JournalChemistry - A European Journal
Volume23
Issue number43
DOIs
Publication statusPublished - Aug 1 2017

Fingerprint

X ray crystallography
Phosphorus
Nuclear magnetic resonance spectroscopy
Conformations
Iron

Keywords

  • ab initio calculations
  • ferrocene
  • heteronuclear NMR spectroscopy
  • phosphorus
  • triphosphanes

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Borucki, S., Kelemen, Z., Maurer, M., Bruhn, C., Nyulászi, L., & Pietschnig, R. (2017). Stereochemical Alignment in Triphospha[3]ferrocenophanes. Chemistry - A European Journal, 23(43), 10438-10450. https://doi.org/10.1002/chem.201701905

Stereochemical Alignment in Triphospha[3]ferrocenophanes. / Borucki, Stefan; Kelemen, Zsolt; Maurer, Martin; Bruhn, Clemens; Nyulászi, L.; Pietschnig, Rudolf.

In: Chemistry - A European Journal, Vol. 23, No. 43, 01.08.2017, p. 10438-10450.

Research output: Contribution to journalArticle

Borucki, S, Kelemen, Z, Maurer, M, Bruhn, C, Nyulászi, L & Pietschnig, R 2017, 'Stereochemical Alignment in Triphospha[3]ferrocenophanes', Chemistry - A European Journal, vol. 23, no. 43, pp. 10438-10450. https://doi.org/10.1002/chem.201701905
Borucki, Stefan ; Kelemen, Zsolt ; Maurer, Martin ; Bruhn, Clemens ; Nyulászi, L. ; Pietschnig, Rudolf. / Stereochemical Alignment in Triphospha[3]ferrocenophanes. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 43. pp. 10438-10450.
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