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Iron(II) complexes of 2,6-di(1-alkylpyrazol-3-yl)pyridine derivatives – The influence of distal substituents on the spin state of the iron centre.
- Source :
-
Polyhedron . Nov2013, Vol. 64, p4-12. 9p. - Publication Year :
- 2013
-
Abstract
- Abstract: 2,6-Di(1-methyl-pyrazol-3-yl)pyridine (LMe), 2,6-di(1-allyl-pyrazol-3-yl)pyridine (LAll), 2,6-di(1-benzyl-pyrazol-3-yl)pyridine (LBz) and di(1-isopropyl-pyrazol-3-yl)pyridine (L i Pr) have been synthesized by alkylation of deprotonated di{1H-pyrazol-3-yl}pyridine (3-bpp), and converted to salts of the corresponding [Fe(LR)2]2+ complexes (R=Me, All, Bz and iPr). Crystal structures of [Fe(LMe)2]X2 (X− =BF4 −, ClO4 − and PF6 −), [Fe(LAll)2][BF4]2, [Fe(LBz)2][BF4]2 and [Fe(L i Pr)2][PF6]2 have been determined at 150K. All of these contain high-spin iron centres except [Fe(LMe)2][BF4]2·xH2O, which is predominantly low-spin at that temperature. All the complexes are high-spin between 5 and 300K as solvent-free bulk powders, and are also high-spin in (CD3)2CO solution between 193 and 293K. This was unexpected, since the parent complex [Fe(3-bpp)2]2+ undergoes spin-crossover in the same solvent with T ½ =247K [40]. The high-spin nature of the [Fe(LR)2]2+ complexes in solution must reflect a subtle balance of steric and electronic factors involving the ligand ‘R’ substituents. [Copyright &y& Elsevier]
Details
- Language :
- English
- ISSN :
- 02775387
- Volume :
- 64
- Database :
- Academic Search Index
- Journal :
- Polyhedron
- Publication Type :
- Academic Journal
- Accession number :
- 90433950
- Full Text :
- https://doi.org/10.1016/j.poly.2013.01.057