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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.

The description of π‐donor amido moieties as ‘weak‐field’ ligands can belie the influence of metal‐ligand covalency on the overall ligand field of coordination complexes, which can in turn influence properties including the magnetic ground state and those of their excited states. In this contribution, the ligand fields of pseudo‐octahedral Ni(II) complexes supported by diarylamido pincer‐type amido ligands – three previously reported examples supported by asymmetric (2‐R‐phenanthridin‐4‐yl)(8‐quinolinyl)amido ligands (R = Cl, CF₃,tBu;^RL¹) along with a new congener bearing a symmetricbis(8‐quinolinyl)amido ligand (BQA;L²) – were investigated in two ways. First, high‐frequency and ‐field electron paramagnetic resonance spectroscopy (HFEPR), SQUID magnetometry, and electronic absorption spectroscopy were used to determine the ligand field parameters. Second, the ability to electrochemically address ligand‐based oxidations despite metal‐centered SOMOs in the parentS=1 paramagnets was investigated, supported by time‐dependent density functional theory (TDDFT) identification of strong intervalence charge‐transfer (IVCT) transitions attributed to electronic communication between two N_amidomoieties mediated by a Ni(II) bridge. These findings are discussed in the broader context of 3d transition metal coordination complexes of weak‐field π‐donor ligands.