2018
DOI: 10.1002/anie.201713209
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Synthesis, Characterization, and Reactivity of Cationic Gold Diarylallenylidene Complexes

Abstract: Methoxide abstraction from gold acetylide complexes of the form (L)Au[η -C≡CC(OMe)ArAr'] (L=IPr, P( Bu) (ortho-biphenyl); Ar/Ar'=C H 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 H NMR analysis. C NMR and IR spectroscopic analysis of these complexes established the arene-dependent delocalization of positive charge on both the… Show more

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Cited by 25 publications
(25 citation statements)
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“…It is noteworthy that for complex a the stretching frequency ν CAu/1‐C2 of 2051 cm −1[4] is still reflective of significant alkyne character. Notably, the precursor featuring a OMe group bound to C 3 has a ν CAu/1‐C2 stretching frequency of 2120 cm −1 , so the observed ν CAu/1‐C2 in the complex shows a shift of merely 69 cm −1 . Overall both this spectroscopic feature and our computational analyses identify Lewis structure III (shown in Figure ) as the most suitable depiction of the bonding scenario in these complexes.…”
Section: Resultsmentioning
confidence: 60%
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“…It is noteworthy that for complex a the stretching frequency ν CAu/1‐C2 of 2051 cm −1[4] is still reflective of significant alkyne character. Notably, the precursor featuring a OMe group bound to C 3 has a ν CAu/1‐C2 stretching frequency of 2120 cm −1 , so the observed ν CAu/1‐C2 in the complex shows a shift of merely 69 cm −1 . Overall both this spectroscopic feature and our computational analyses identify Lewis structure III (shown in Figure ) as the most suitable depiction of the bonding scenario in these complexes.…”
Section: Resultsmentioning
confidence: 60%
“… Correlation plots between the experimentally determined ν CAu/1‐C2 stretching frequency and A) the overlap with IBOs associated with the sum of the aromatic substituents [black squares] and the relevant π‐bond with C 3 [red diamonds] and B) the total Charge Transfer (CT net ) [black squares] and the associated to the total perpendicular π ⊥ ‐backdonation [red diamonds].…”
Section: Resultsmentioning
confidence: 99%
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