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Abstract Coordination complexes of general formulatrans‐[MX₂(R₂ECH₂CH₂ER₂)₂] (M^II=Ti, V, Cr, Mn; E=N or P; R=alkyl or aryl) are a cornerstone of coordination and organometallic chemistry. We investigate the electronic properties of two such complexes,trans‐[VCl₂(tmeda)₂] andtrans‐[VCl₂(dmpe)₂], which thus representtrans‐[MX₂(R₂ECH₂CH₂ER₂)₂] where M=V, X=Cl, R=Me and E=N (tmeda) and P (dmpe). These V^IIcomplexes haveS=3/2 ground states, as expected for octahedral d³. Their tetragonal distortion leads to zero‐field splitting (zfs) that is modest in magnitude (D≈0.3 cm⁻¹) relative to analogousS=1 Ti^IIand Cr^IIcomplexes. This parameter was determined from conventional EPR spectroscopy, but more effectively from high‐frequency and ‐field EPR (HFEPR) that determined the sign ofDas negative for the diamine complex, but positive for the diphosphine, which information had not been known for anytrans‐[VX₂(R₂ECH₂CH₂ER₂)₂] systems. The ligand‐field parameters oftrans‐[VCl₂(tmeda)₂] andtrans‐[VCl₂(dmpe)₂] are obtained using both classical theory andab initioquantum chemical theory. The results shed light not only on the electronic structure of V^IIin this environment, but also on differences between N and P donor ligands, a key comparison in coordination chemistry.