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29Si NMR spectroscopy was employed to evaluate the electron donor properties of the (L)Au fragments in the cationic gold (β,β‐disilyl)vinylidene complexes [(L)Au=C=CSi(Me)2CH2CH2Si(Me)2]+B(C6F5)4− [L=P(tBu)2o‐biphenyl or NHC] relative to the p‐substituted aryl group in the α‐aryl‐(β,β‐disilyl)vinyl cations [(p‐C6H4X)‐C= CSi(Me)2CH2CH2Si(Me)2]+B(C6F5)4−. Similarly, 19F NMR was employed to evaluate...