Synthesis, Characterization, and Reactivity of Cationic Gold Diarylallenylidene Complexes.
Methoxide abstraction from gold acetylide complexes of the form (L)Au[η1 -C≡CC(OMe)ArAr'] (L=IPr, P(t Bu)2 (ortho-biphenyl); Ar/Ar'=C6 H4 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=CPh2 ]+ OTf- reacted with heteroatom nucleophiles at the allenylidene C1 and/or C3 carbon atom.
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