Structural identification of the factors that prevent an electronic spin-state crossover in Fe[(C6H5)B(3-Mepz)3]2 (pz=pyrazolyl ring)

Autor: Daniel L. Reger, Fernande Grandjean, J. Derek Elgin, Gary J. Long, Leila Rebbouh, Mark D. Smith
Rok vydání: 2006
Předmět:
Zdroj: Polyhedron. 25:2616-2622
ISSN: 0277-5387
Popis: The synthesis, structural, magnetic, and Mossbauer spectral properties of Fe[(C6H5)B(3-Mepz)3]2 (2, pz = pyrazolyl ring) are reported. The single crystal X-ray structural results indicate that at both 294 and 90 K Fe[(C6H5)B(3-Mepz)3]2 (2) has a distorted octahedral iron(II) coordination environment with Fe–N bond distances that average ca. 2.18 A, distances that clearly indicate the high-spin nature of the complex at these temperatures. Both the magnetic and Mossbauer spectral results indicate that Fe[(C6H5)B(3-Mepz)3]2 (2) remains high-spin down to 4 K. This result is surprising because the closely related Fe[(p-R-C6H4)B(3-Mepz)3]2 [R = I, C C H, C C SiMe3, or C C C6H5] complexes do exhibit electronic spin-state changes on cooling. The absence of a spin-state crossover in Fe[(C6H5)B(3-Mepz)3]2 (2) is the result of its molecular structure in which the three pyrazolyl rings of each tridentate ligand are highly twisted away from an ideal C3v coordination symmetry, a twisting distortion that favors the high-spin form of the complex with longer Fe–N bond distances.
Databáze: OpenAIRE