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Synthesis, Characterization, and Reactivity of Cationic Gold Diarylallenylidene Complexes
Author(s) -
Kim Nana,
Widenhoefer Ross A.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201713209
Subject(s) - acetylide , chemistry , cationic polymerization , heteroatom , trimethylsilyl trifluoromethanesulfonate , reactivity (psychology) , trifluoromethanesulfonate , nucleophile , electrophile , medicinal chemistry , delocalized electron , heteronuclear molecule , trimethylsilyl , methoxide , nuclear magnetic resonance spectroscopy , stereochemistry , polymer chemistry , organic chemistry , ion , ring (chemistry) , catalysis , medicine , alternative medicine , pathology
Methoxide abstraction from gold acetylide complexes of the form (L)Au[η 1 ‐C≡CC(OMe)ArAr′] (L=IPr, P( t Bu) 2 ( ortho ‐biphenyl); Ar/Ar′=C 6 H 4 X where X=H, Cl, Me, OMe) with trimethylsilyl trifluoromethanesulfonate (TMSOTf) at −78 °C resulted in the formation of the corresponding cationic gold diarylallenylidene complexes [(L)Au=C=C=CArAr′] + OTf − in ≥85±5 % yield according to 1 H NMR analysis. 13 C NMR and IR spectroscopic analysis of these complexes established the arene‐dependent delocalization of positive charge on both the C1 and C3 allenylidene carbon atoms. The diphenylallenylidene complex [(IPr)Au=C=C=CPh 2 ] + OTf − reacted with heteroatom nucleophiles at the allenylidene C1 and/or C3 carbon atom.