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Converging and Diverging Synthetic Strategies to Tetradentate (N,N′)-Diaminomethyl,(P,P′)-Ferrocenyl Ligands: Influence of tert-Butyl Groups on Ferrocene Backbone Conformation
journal contribution
posted on 2015-10-26, 00:00 authored by Fatima Allouch, Nejib Dwadnia, Nikolay V. Vologdin, Yurii
V. Svyaschenko, Hélène Cattey, Marie-José Penouilh, Julien Roger, Daoud Naoufal, Ridha Ben Salem, Nadine Pirio, Jean-Cyrille HiersoHexasubstituted
hybrid tetradentate (N,N′,P,P′)-ferrocenes
bearing phosphino and aminomethyl groups, plus hindering tert-butyl moieties, were synthesized by using two different strategies:
a “diverging” synthesis involving successive functionalization
of preformed di-tert-butylated ferrocene and a “converging”
assembly of the species from appropriately substituted cyclopentadienyl
rings. While the new cyclopentadienyl salts formed are of interest,
their assembly with iron dichloride used as a “converging”
way to produce tetradentate ferrocene ligands presented several drawbacks.
Conversely, the synthesis of new tert-butylated (aminomethyl)ferrocene
derivatives was found convenient to further form (N,N′)-aminomethyl,(P,P′)-tert-butylated-ferrocenyl diphosphines
by N-directed ortho-metalation. The novel N2-didentate and N2P2-tetradentate tert-butylated ferrocene compounds were all synthesized in good to high
yields (48–96%) and tolerated aryl, alkyl, and heteroaryl phosphino
groups as substituents on nitrogen and phosphorus atoms. They were
characterized by X-ray diffraction and multinuclear NMR (1H, 13C, 31P, 15N). We observed the
conformation control provided to rac-(N,N′)-diaminomethyl-(P,P′)-tert-butylated-ferrocenyldiphosphines
with in particular the systematic near-eclipsed conformation of aminomethyl
groups. This conformation is at the origin of the unexpected formation
at RT of a zwitterionic cyclopalladate from an (aminomethyl)ferrocene
derivative, arising from intramolecular Cp-proton transfer to the
proximate free amino group by simple C–H activation reaction
in the presence of palladium dichloride.