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New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures
Author(s) -
Fard Mahmood Azizpoor,
Khalili Najafabadi Bahareh,
Hesari Mahdi,
Workentin Mark S.,
Corrigan John F.
Publication year - 2014
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.201400185
Subject(s) - trimethylsilyl , denticity , chalcogen , silylation , reagent , chemistry , aryl , crystallography , electrospray ionization , nuclear magnetic resonance spectroscopy , crystal structure , medicinal chemistry , mass spectrometry , stereochemistry , alkyl , organic chemistry , catalysis , chromatography
A series of polychalcogenotrimethylsilane complexes Ar(CH 2 ESiMe 3 ) n , (Ar=aryl; E=S, Se; n =2, 3, and 4) can be prepared from the corresponding polyorganobromide and M[ESiMe 3 ] (M=Na, Li). These represent the first examples of the incorporation of such a large number of reactive ESiMe 3 moieties onto an organic molecular framework. They are shown to be convenient reagents for the preparation of the polyferrocenylseleno‐ and thioesters from ferrocenoyl chloride. The synthesis, structures, and spectroscopic properties of the new silyl chalcogen complexes 1,4‐(Me 3 SiECH 2 ) 2 (C 6 Me 4 ) (E=S, 1 ; E=Se, 2 ), 1,3,5‐(Me 3 SiECH 2 ) 3 (C 6 Me 3 ) (E=S, 3 ; E=Se, 4 ) and 1,2,4,5‐(Me 3 SiECH 2 ) 4 (C 6 H 2 ) (E=S, 5 ; E=Se, 6 ) and the polyferrocenyl chalcogenoesters [1,4‐{FcC(O)ECH 2 } 2 (C 6 Me 4 )] (E=S, 7 ; E=Se, 8 ), [1,3,5‐{FcC(O)ECH 2 } 3 (C 6 Me 3 )] (E=S, 9 ; E=Se, 10 ) and [1,2,4,5‐{FcC(O)ECH 2 } 4 (C 6 H 2 )] (E=S, 11 illustrated; E=Se, 12 ) are reported. The new polysilylated reagents and polyferrocenyl chalcogenoesters have been characterized by multinuclear NMR spectroscopy ( 1 H, 13 C, 77 Se), electrospray ionization mass spectrometry and, for complexes 1 , 2 , 3 , 4 , 7 , 8 , and 11 , single‐crystal X‐ray diffraction. The cyclic voltammograms of complexes 7 – 11 are presented.