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Abstract We introduce the heterocumulene ligand [(Ad)NCC(^tBu)]⁻(Ad=1‐adamantyl (C₁₀H₁₅),^tBu=tert‐butyl, (C₄H₉)), which can adopt two forms, the azaalleneyl and ynamide. This ligand platform can undergo a reversible chelotropic shift using Brønsted acid‐base chemistry, which promotes an unprecedented spin‐state change of the [V^III] ion. These unique scaffolds are prepared via addition of 1‐adamantyl isonitrile (C≡NAd) across the alkylidyne in complexes [(BDI)V≡C^tBu(OTf)] (A) (BDI⁻=ArNC(CH₃)CHC(CH₃)NAr), Ar=2,6‐ⁱPr₂C₆H₃) and [(dBDI)V≡C^tBu(OEt₂)] (B) (dBDI²⁻=ArNC(CH₃)CHC(CH₂)NAr). ComplexAreacts with C≡NAd, to generate the high‐spin [V^III] complex with a κ¹‐N‐ynamide ligand, [(BDI)V{κ¹‐N‐(Ad)NCC(^tBu)}(OTf)] (1). Conversely,Breacts with C≡NAd to generate a low‐spin [V^III] diamagnetic complex having a chelated κ²‐C,N‐azaalleneyl ligand, [(dBDI)V{κ²‐N,C‐(Ad)NCC(^tBu)}] (2). Theoretical studies have been applied to better understand the mechanism of formation of2and the electronic reconfiguration upon structural rearrangement by the alteration of ligand denticity between1and2.