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Stereochemical Alignment in Triphospha[3]ferrocenophanes
Author(s) -
Borucki Stefan,
Kelemen Zsolt,
Maurer Martin,
Bruhn Clemens,
Nyulászi László,
Pietschnig Rudolf
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701905
Subject(s) - diastereomer , stereocenter , chemistry , heteronuclear molecule , stereochemistry , nuclear magnetic resonance spectroscopy , crystallography , enantioselective synthesis , organic chemistry , catalysis
A series of triphospha[3]ferrocenophanes of the type Fe(C 5 H 4 ‐P t Bu) 2 PX with X=H, F, Cl, Br, I, NEt 2 , t Bu 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(C 5 H 4 ) 2 (P t Bu) 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(C 5 H 4 ) 2 (PPh) 3 .