title: Synthesis, structures, and dearomatization by deprotonation of iron complexes featuring bipyridine-based PNN pincer ligands.
abstract: The synthesis and characterization of new iron pincer complexes bearing bipyridine-based PNN ligands is reported. Three phosphine-substituted pincer ligands, namely, the known (t)Bu-PNN (6-((di-tert-butylphosphino)methyl)-2,2'-bipyridine) and the two new (i)Pr-PNN (6-((di-iso-propylphosphino)methyl)-2,2'-bipyridine) and Ph-PNN (6-((diphenylphosphino)methyl)-2,2'-bipyridine) ligands were synthesized and studied in ligation reactions with iron(II) chloride and bromide. These reactions lead to the formation of two types of complexes: mono-chelated neutral complexes of the type [(R-PNN)Fe(X)2] and bis-chelated dicationic complexes of the type [(R-PNN)2Fe](2+). The complexes [(R-PNN)Fe(X)2] (1: R = (t)Bu, X = Cl, 2: R = (t)Bu, X = Br, 3: R = (i)Pr, X = Cl, and 4: R = (i)Pr, X = Br) are readily prepared from reactions of FeX2 with the free R-PNN ligand in a 1:1 ratio. Magnetic susceptibility measurements show that these complexes have a high-spin ground state (S = 2) at room temperature. Employing a 2-fold or higher excess of (i)Pr-PNN, diamagnetic hexacoordinated dicationic complexes of the type [((i)Pr-PNN)2Fe](X)2 (5: X = Cl, and 6: X = Br) are formed. The reactions of Ph-PNN with FeX2 in a 1:1 ratio lead to similar complexes of the type [(Ph-PNN)2Fe](FeX4) (7: X = Cl, and 8: X = Br). Single crystal X-ray studies of 1, 2, 4, 6, and 8 do not indicate electron transfer from the Fe(II) centers to the neutral bipyridine unit based on the determined bond lengths. Density functional theory (DFT) calculations were performed to compare the relative energies of the mono- and bis-chelated complexes. The doubly deprotonated complexes [(R-PNN*)2Fe] (9: R = (i)Pr, and 10: R = Ph) were synthesized by reactions of the dicationic complexes 6 and 8 with KO(t)Bu. The dearomatized nature of the central pyridine of the pincer ligand was established by X-ray diffraction analysis of single crystals of 10. Reactivity studies show that 9 and 10 have a slightly different behavior in protonation reactions.
authors.affiliation: Department of Organic Chemistry, Weizmann Institute of Science, 76100 Rehovot, Israel.
authors.forename: Thomas
authors.initials: T
authors.lastname: Zell
authors.forename: Robert
authors.initials: R
authors.lastname: Langer
authors.forename: Mark A
authors.initials: MA
authors.lastname: Iron
authors.forename: Leonid
authors.initials: L
authors.lastname: Konstantinovski
authors.forename: Linda J W
authors.initials: LJ
authors.lastname: Shimon
authors.forename: Yael
authors.initials: Y
authors.lastname: Diskin-Posner
authors.forename: Gregory
authors.initials: G
authors.lastname: Leitus
authors.forename: Ekambaram
authors.initials: E
authors.lastname: Balaraman
authors.forename: Yehoshoa
authors.initials: Y
authors.lastname: Ben-David
authors.forename: David
authors.initials: D
authors.lastname: Milstein
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry*; D005296:Ferrous Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011522:Protons
chemical_list: D005296:Ferrous Compounds; D008024:Ligands; D011522:Protons; D015082:2,2'-Dipyridyl