Abstract
The isolation and structural characterization of [(terpy)MnIII(N3)3], complex 1, is reported (terpy = 2,2′:6′,2-″terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer[(terpy)(H2O)MnIII(O) 2-MnIV(OH2)(terpy)] (NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) Å b = 8.9007(2) Å, c = 12.109(2) Å, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)° and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The vasym(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm-1 with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1 with a weaker broad band at 2046 cm-1. The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (±0.01) cm-1, E = 0.48 (±0.01) cm-1, E′= 0.53 (±0.01) cm-1, gx = 2.00 (±0.005), gy = 1.98 (±0.005), gz = 2.01 (±0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D <0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (±0.01) cm-1, E = 0.51 (±0.01) cm-1, gx = 2.00 (±0.005), gy = L98 (±0.005), and g, = 2.01 (±0.005).
| Original language | English |
|---|---|
| Pages (from-to) | 1698-1703 |
| Number of pages | 6 |
| Journal | Inorganic Chemistry |
| Volume | 40 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - Mar 26 2001 |
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High-frequency EPR study of a new mononuclear manganese(III) complex : [(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine). / Limburg, J.; Vrettos, J. S.; Crabtree, R. H.; Brudvig, Gary W; De Paula, J. C.; Hassan, A.; Barra, A. L.; Duboc-Toia, C.; Collomb, M. N.
In: Inorganic Chemistry, Vol. 40, No. 7, 26.03.2001, p. 1698-1703.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - High-frequency EPR study of a new mononuclear manganese(III) complex
T2 - [(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine)
AU - Limburg, J.
AU - Vrettos, J. S.
AU - Crabtree, R. H.
AU - Brudvig, Gary W
AU - De Paula, J. C.
AU - Hassan, A.
AU - Barra, A. L.
AU - Duboc-Toia, C.
AU - Collomb, M. N.
PY - 2001/3/26
Y1 - 2001/3/26
N2 - The isolation and structural characterization of [(terpy)MnIII(N3)3], complex 1, is reported (terpy = 2,2′:6′,2-″terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer[(terpy)(H2O)MnIII(O) 2-MnIV(OH2)(terpy)] (NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) Å b = 8.9007(2) Å, c = 12.109(2) Å, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)° and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The vasym(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm-1 with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1 with a weaker broad band at 2046 cm-1. The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (±0.01) cm-1, E = 0.48 (±0.01) cm-1, E′= 0.53 (±0.01) cm-1, gx = 2.00 (±0.005), gy = 1.98 (±0.005), gz = 2.01 (±0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D <0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (±0.01) cm-1, E = 0.51 (±0.01) cm-1, gx = 2.00 (±0.005), gy = L98 (±0.005), and g, = 2.01 (±0.005).
AB - The isolation and structural characterization of [(terpy)MnIII(N3)3], complex 1, is reported (terpy = 2,2′:6′,2-″terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer[(terpy)(H2O)MnIII(O) 2-MnIV(OH2)(terpy)] (NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) Å b = 8.9007(2) Å, c = 12.109(2) Å, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)° and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The vasym(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm-1 with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1 with a weaker broad band at 2046 cm-1. The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (±0.01) cm-1, E = 0.48 (±0.01) cm-1, E′= 0.53 (±0.01) cm-1, gx = 2.00 (±0.005), gy = 1.98 (±0.005), gz = 2.01 (±0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D <0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (±0.01) cm-1, E = 0.51 (±0.01) cm-1, gx = 2.00 (±0.005), gy = L98 (±0.005), and g, = 2.01 (±0.005).
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U2 - 10.1021/ic001118j
DO - 10.1021/ic001118j
M3 - Article
VL - 40
SP - 1698
EP - 1703
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 7
ER -