title: Synthesis and catalytic properties in olefin epoxidation of novel iron(II) complexes with pyridine-containing macrocycles bearing an aminopropyl pendant arm.
abstract: Three novel iron(II) complexes with pyridine-containing macrocycles bearing an aminopropyl pendant arm were synthesized and characterized. Crystal structures of two of the complexes revealed high-spin iron(II) centers coordinated to the five ligand nitrogen atoms with no coordination of either the solvent molecules or anions, resulting in an unusual square-pyramidal geometry. Related tetradentate ligand CRH formed a low-spin iron(II) complex (meso form was structurally characterized) with a planar arrangement of the four nitrogen atoms from the macrocycle and two axial acetonitrile molecules. Similarly to the corresponding nickel and copper complexes of the pentadentate ligands, the protonation of the amino group on the ligand arm in iron(II) complexes was found to be reversible. Spectral changes and magnetic susceptibility measurements indicated that a change in the geometry and spin state of the metal center is associated with this acid-base process. In the presence of noncoordinating acids (e.g., triflic acid), these complexes, as well as their nonmethylated analogue, can efficiently catalyze the epoxidation of cyclooctene and 1-decene under mild conditions, using hydrogen peroxide as the oxidant. However, in the deprotonated form or in the presence of coordinating acids like HCl, no epoxidation occurs.
authors.affiliation: Department of Chemistry, Tufts University, Medford, Massachusetts 02155, USA.
authors.forename: Sonia
authors.initials: S
authors.lastname: Taktak
authors.forename: Wanhua
authors.initials: W
authors.lastname: Ye
authors.forename: Aida M
authors.initials: AM
authors.lastname: Herrera
authors.forename: Elena V
authors.initials: EV
authors.lastname: Rybak-Akimova
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D034242:Cyclooctanes / Q000737:chemistry; D004563:Electrochemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D005296:Ferrous Compounds / Q000737:chemistry*; D047028:Macrocyclic Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D011725:Pyridines / Q000737:chemistry*
chemical_list: D000475:Alkenes; D034242:Cyclooctanes; D004852:Epoxy Compounds; D005296:Ferrous Compounds; D047028:Macrocyclic Compounds; D011725:Pyridines; C474479:cyclooctane; C023666:pyridine