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Distannabarrelenes with Three Coordinated Sn II Atoms
Author(s) -
Sharma Mahendra K.,
Glodde Timo,
Neumann Beate,
Stammler HansGeorg,
Ghadwal Rajendra S.
Publication year - 2020
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.202001432
Subject(s) - lone pair , valence (chemistry) , chemistry , cationic polymerization , sn2 reaction , crystallography , sulfur , moiety , nuclear magnetic resonance spectroscopy , stereochemistry , molecule , organic chemistry
Crystalline 1,4‐distannabarrelene compounds [(ADC Ar ) 3 Sn 2 ]SnCl 3 ( 3 ‐ Ar ) (ADC Ar ={ArC(NDipp) 2 CC}; Dipp=2,6‐ i Pr 2 C 6 H 3 , Ar=Ph or DMP; DMP=4‐Me 2 NC 6 H 4 ) derived from anionic dicarbenes Li(ADC Ar ) ( 2 ‐ Ar ) (Ar=Ph or DMP) have been reported. The cationic moiety of 3 ‐ Ar features a barrelene framework with three coordinated Sn II atoms at the 1,4‐positions, whereas the anionic unit SnCl 3 is formally derived from SnCl 2 and chloride ion. The all carbon substituted bis‐stannylenes 3 ‐ Ar have been characterized by NMR spectroscopy and X‐ray diffraction. DFT calculations reveal that the HOMO of 3 ‐ Ph ( ϵ =−6.40 eV) is mainly the lone‐pair orbital at the Sn II atoms of the barrelene unit. 3 ‐ Ar readily react with sulfur and selenium to afford the mixed‐valence Sn II /Sn IV compounds [(ADC Ar ) 3 SnSn(E)](SnCl 6 ) 0.5 (E=S 4 ‐ Ar , Ar=Ph or DMP; E=Se 5 ‐ Ph ).