A synthetic, structural, magnetic, and spectral study of several [Fe[tris(pyrazolyl)methane]2](BF4)2 complexes: observation of an unusual spin-state crossover.
The complexes [Fe[HC(3,5-Me2pz)3]2](BF4)2 (1), [Fe[HC(pz)3]2](BF4)2 (2), and [Fe[PhC(pz)2(py)]2](BF4)2 (3) (pz = 1-pyrazolyl ring, py = pyridyl ring) have been synthesized by the reaction of the appropriate ligand with Fe(BF4)2.6H2O. Complex 1 is high-spin in the solid state and in solution at 298 K. In the solid phase, it undergoes a decrease in magnetic moment at lower temperatures, changing at ca. 206 K to a mixture of high-spin and low-spin forms, a spin-state mixture that does not change upon subsequent cooling to 5 K. Crystallographically, there is only one iron(II) site in the ambient-temperature solid-state structure, a structure that clearly shows the complex is high-spin. Mössbauer spectral studies show conclusively that the magnetic moment change observed at lower temperatures arises from the complex changing from a high-spin state at higher temperatures to a 50:50 mixture of high-spin and low-spin states at lower temperatures. Complexes 2 and 3 are low-spin in the solid phase at room temperature. Complex 2 in the solid phase gradually changes over to the high-spin state upon heating above 295 K and is completely high-spin at ca. 470 K. In solution, variable-temperature 1H NMR spectra of 2 show both high-spin and low-spin forms are present, with the percentage of the paramagnetic form increasing as the temperature increases. Complex 3 is low-spin at all temperatures studied in both the solid phase and solution. An X-ray absorption spectral study has been undertaken to investigate the electronic spin states of [Fe[HC(3,5-Me2pz)3]2](BF4)2 and [Fe[HC(pz)3]2](BF4)2. Crystallographic information: 2 is monoclinic, P2(1)/n, a = 10.1891(2) A, b = 7.6223(2) A, c = 17.2411(4) A, beta = 100.7733(12) degrees, Z = 2; 3 is triclinic, P1, a = 12.4769(2) A, b = 12.7449(2) A, c = 13.0215(2) A, alpha = 83.0105(8) degrees, beta = 84.5554(7) degrees, gamma = 62.5797(2) degrees, Z = 2.
Institut de Physique, B5, Université de Liège, B-4000 Sart-Tilman, Belgium.
D L
DL
Reger
C A
CA
Little
A L
AL
Rheingold
M
M
Lam
L M
LM
Liable-Sands
B
B
Rhagitan
T
T
Concolino
A
A
Mohan
G J
GJ
Long
V
V
Briois
F
F
Grandjean
D003461:Crystallography; D005296:Ferrous Compounds / Q000737:chemistry*; D015394:Molecular Structure; D011720:Pyrazoles / Q000737:chemistry*; D013057:Spectrum Analysis
C425864:Fe(tris(pyrazolyl)methane)2(BF4)2; D005296:Ferrous Compounds; D011720:Pyrazoles