TY - JOUR

T1 - Nitridocyanometalates of CrV, MnV, and MnVI

AU - Bendix, Jesper

AU - Meyer, Karsten

AU - Weyhermüller, Thomas

AU - Bill, Eckhard

AU - Metzler-Nolte, Nils

AU - Wieghardt, Karl

PY - 1998/12/1

Y1 - 1998/12/1

N2 - Reaction of [CrV(N)(salen)]·CH3NO2 and [MnV(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[CrV(N)(CN)5] (1); [N(CH3)4]2Na[CrV(N)(CN) 5]·H2O (1a) and pink-violet crystals of Cs2Na[MnV(N)(CN)5] (4); and [N(CH3)4]2Na[MnV(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 = CrV (2), MnV (5)). From pyridine solutions of 2 and 5 the six-coordinate species [PPh4]2[M(N)-(CN)4(py)]·H 2O· py (M = CrV (3), MnV (6)) crystallize. Complexes 1, 1a, 2, and 3 are paramagnetic (1.8 ± 0.1 μB 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 [MnVI(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)) Å3, 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) Å3, and Z=2. The complexes have been characterized by 13C and 15N NMR, UV-vis, EPR, IR/Raman, and MCD spectroscopies.

AB - Reaction of [CrV(N)(salen)]·CH3NO2 and [MnV(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[CrV(N)(CN)5] (1); [N(CH3)4]2Na[CrV(N)(CN) 5]·H2O (1a) and pink-violet crystals of Cs2Na[MnV(N)(CN)5] (4); and [N(CH3)4]2Na[MnV(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 = CrV (2), MnV (5)). From pyridine solutions of 2 and 5 the six-coordinate species [PPh4]2[M(N)-(CN)4(py)]·H 2O· py (M = CrV (3), MnV (6)) crystallize. Complexes 1, 1a, 2, and 3 are paramagnetic (1.8 ± 0.1 μB 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 [MnVI(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)) Å3, 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) Å3, and Z=2. The complexes have been characterized by 13C and 15N NMR, UV-vis, EPR, IR/Raman, and MCD spectroscopies.

UR - http://www.scopus.com/inward/record.url?scp=0001593171&partnerID=8YFLogxK

M3 - Journal article

AN - SCOPUS:0001593171

VL - 37

SP - 1767

EP - 1775

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 8

ER -