TY - JOUR

T1 - Molecular and electronic structure of nitridocyanometalates of chromium(V) and manganese(V)

T2 - A combined experimental and DFT study

AU - Bendix, Jesper

AU - Deeth, Robert J.

AU - Weyhermüller, Thomas

AU - Bill, Eckhard

AU - Wieghardt, Karl

PY - 2000/3/6

Y1 - 2000/3/6

N2 - The six-coordinate complexes [M(N)(CN)5]3- (M = Cr, Mn) have been isolated as salts of robust rhodium amine complexes. [Rh(en)3][Mn(N)(CN)5]·H2O (1) and [Rh(tn)3] [Cr(N)(CN)5]·2H2O (2) have been characterized by single-crystal X-ray crystallography: 1 crystallizes in the hexagonal space group P63 with a = b = 15.810(2) Å, c = 13.844(3) Å, V = 2996.8(8) Å3, and Z = 6; 2 crystallizes in the orthorhombic space group Pbcn with a = 9.723(1) Å, b = 14.564(2) Å, c = 31.498(4) Å, V = 4460.3(8) Å3, and Z = 8. In 1, all the anions are oriented with their Mn≡N directions almost coparallel to the crystallographic 3-fold axis. Polarized single-crystal UV-vis spectroscopy of I confirms the validity of the Jorgensen-Ballhausen-Gray d-orbital splitting scheme with the lowest energy transition being d(xy) → {d(yz),d(zx)}. Single-crystal EPR spectroscopy of [Cr(N)(CN)5]3- dilated into 1 shows the hyperfine (53Cr) and super-hyperfine (14N) tensors to be quite anisotropic with different major axes. For the hyperfine interaction we observe A is parallel with > A is perpendicular to, whereas, for the super-hyperfine interaction to the terminal nitrido ligand, the reverse ordering is found: A is perpendicular to > A is parallel to. The complexes [M(N)(CN)5]3-, trans-[M(N)(CN)4(py)]2-, and [M(N)(CN)4]2- (M = Cr, Mn) were investigated by DFT methods. Good reproduction of the molecular structures, vibrational, and UV-vis spectra was obtained. However, pronounced differences between local density and gradient corrected functionals were observed in the description of the weak bonding to the ligands trans to the nitrido ligand. For the five-coordinate [M(N)(CN)4]2- complexes the LUMO is predicted to be a strongly admixed d(z)2(M)-p(z)(M) hybrid.

AB - The six-coordinate complexes [M(N)(CN)5]3- (M = Cr, Mn) have been isolated as salts of robust rhodium amine complexes. [Rh(en)3][Mn(N)(CN)5]·H2O (1) and [Rh(tn)3] [Cr(N)(CN)5]·2H2O (2) have been characterized by single-crystal X-ray crystallography: 1 crystallizes in the hexagonal space group P63 with a = b = 15.810(2) Å, c = 13.844(3) Å, V = 2996.8(8) Å3, and Z = 6; 2 crystallizes in the orthorhombic space group Pbcn with a = 9.723(1) Å, b = 14.564(2) Å, c = 31.498(4) Å, V = 4460.3(8) Å3, and Z = 8. In 1, all the anions are oriented with their Mn≡N directions almost coparallel to the crystallographic 3-fold axis. Polarized single-crystal UV-vis spectroscopy of I confirms the validity of the Jorgensen-Ballhausen-Gray d-orbital splitting scheme with the lowest energy transition being d(xy) → {d(yz),d(zx)}. Single-crystal EPR spectroscopy of [Cr(N)(CN)5]3- dilated into 1 shows the hyperfine (53Cr) and super-hyperfine (14N) tensors to be quite anisotropic with different major axes. For the hyperfine interaction we observe A is parallel with > A is perpendicular to, whereas, for the super-hyperfine interaction to the terminal nitrido ligand, the reverse ordering is found: A is perpendicular to > A is parallel to. The complexes [M(N)(CN)5]3-, trans-[M(N)(CN)4(py)]2-, and [M(N)(CN)4]2- (M = Cr, Mn) were investigated by DFT methods. Good reproduction of the molecular structures, vibrational, and UV-vis spectra was obtained. However, pronounced differences between local density and gradient corrected functionals were observed in the description of the weak bonding to the ligands trans to the nitrido ligand. For the five-coordinate [M(N)(CN)4]2- complexes the LUMO is predicted to be a strongly admixed d(z)2(M)-p(z)(M) hybrid.

UR - http://www.scopus.com/inward/record.url?scp=0034610965&partnerID=8YFLogxK

U2 - 10.1021/ic990971j

DO - 10.1021/ic990971j

M3 - Journal article

C2 - 12526371

AN - SCOPUS:0034610965

VL - 39

SP - 930

EP - 938

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -