Reaction of [Cr^V(N)(salen)]·CH₃NO₂ and [Mn^V(N)(salen)] in dimethylformamide or a methanol/water mixture with an aqueous solution of NaCN and CsCl or [N(CH₃)₄]Cl at elevated temperatures affords in good yields, respectively, yellow microcrystalline compounds of Cs₂Na[Cr^V(N)(CN)₅] (1); [N(CH₃)₄]₂Na[Cr^V(N)(CN) ₅]·H₂O (1a) and pink-violet crystals of Cs₂Na[Mn^V(N)(CN)₅] (4); and [N(CH₃)₄]₂Na[Mn^V(N)(CN) ₅]·H₂O (4a). These six-coordinate nitridopentacyanometalates contain a terminal M≡N unit and a labile cyano group in trans position. Recrystallization from water and addition of [PPh₄]Cl yields the five-coordinate species [PPh₄]₂[M(N)(CN)₄]· 2H₂O (M = Cr^V (2), Mn^V (5)). From pyridine solutions of 2 and 5 the six-coordinate species [PPh₄]₂[M(N)-(CN)₄(py)]·H ₂O· py (M = Cr^V (3), Mn^V (6)) crystallize. Complexes 1, 1a, 2, and 3 are paramagnetic (1.8 ± 0.1 μ_B at 298 K; d¹) whereas 4, 4a, 5, and 6 have a low-spin d² ground state. Electrochemically, 5 can be reversibly one-electron-oxidized in CH₃CN with formation of a relatively stable [Mn^VI(N)(CN)₄]^- anion. Complexes 3, 5, and 6 have been characterized by single-crystal X-ray crystallography: 3 and 6 are isostructural and crystallize in the orthorhombic space group Pnma with a = 17.336(3) (17.254(3)) Å , b = 23.019(4) (22.873(4)) Å, c = 13.563(2) (13.490(2)) Å, V = 5412(2) (5324(2)) ų, and Z = 4 (4) (values in parentheses refer to 6); 5 crystallizes in the triclinic space group P1̄ with a = 12.050(1), b= 12.310(1), c = 16.685(2) Å, α = 97.88(2)°, β = 109.33(2)°, γ = 90.55(2)°, V = 2309.4(4) ų, and Z=2. The complexes have been characterized by ¹³C and ¹⁵N NMR, UV-vis, EPR, IR/Raman, and MCD spectroscopies.