title: Neutral-ligand complexes of bis(imino)pyridine iron: synthesis, structure, and spectroscopy.
abstract: A family of bis(imino)pyridine iron neutral-ligand derivatives, ((iPr)PDI)FeL(n) ((iPr)PDI = 2,6-(2,6-iPr2-C6H3N=CMe)2C6H3N), has been synthesized from the corresponding bis(dinitrogen) complex, ((iPr)PDI)Fe(N2)2. When L is a strong-field ligand such as tBuNC or a chelating alkyl diphosphine such as DEPE (DEPE = 1,2-bis(diethylphosphino)ethane), a five-coordinate, diamagnetic compound results with no spectroscopic evidence for mixing of paramagnetic states. Reducing the field strength of the neutral donor to principally sigma-type ligands such as tBuNH2 or THT (THT = tetrahydrothiophene) also yielded diamagnetic compounds. However, the 1H NMR chemical shifts of the in-plane bis(imino)pyridine hydrogens exhibit a large chemical shift dispersion indicative of temperature-independent paramagnetism (TIP) arising from mixing of an S = 1 excited state via spin-orbit coupling. Metrical data from X-ray diffraction establish bis(imino)pyridine chelate reduction for each structural type, while Mössbauer parameters and NMR spectroscopic data differentiate the spin states of the iron and identify contributions from paramagnetic excited states.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA.
authors.forename: Suzanne C
authors.initials: SC
authors.lastname: Bart
authors.forename: Emil
authors.initials: E
authors.lastname: Lobkovsky
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Chirik
mesh_terms: D007097:Imines / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011725:Pyridines / Q000138:chemical synthesis / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D013057:Spectrum Analysis
chemical_list: D007097:Imines; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D012996:Solutions; D007501:Iron