title: Synthesis with structural and electronic characterization of homoleptic Fe(II)- and Fe(III)-fluorinated phenolate complexes.
abstract: Four Fe(III) compounds and one Fe(II) compound containing mononuclear, homoleptic, fluorinated phenolate anions of the form [Fe(OAr)(m)](n-) have been prepared in which Ar(F) = C(6)F(5) and Ar' = 3,5-C(6)(CF(3))(2)H(3): (Ph(4)P)(2)[Fe(OAr(F))(5)], 1, (Me(4)N)(2)[Fe(OAr(F))(5)], 2, {K(18-crown-6)}(2)[Fe(OAr(F))(5)], 3a, {K(18-crown-6)}(2)[Fe(OAr')(5)], 3b, and {K(18-crown-6)}(2)[Fe(OAr(F))(4)], 6. Two dinuclear Fe(III) compounds have also been prepared: {K(18-crown-6)}(2)[(OAr(F))(3)Fe(μ(2)-O)Fe(OAr(F))(3)], 4, and {K(18-crown-6)}(2)[(OAr(F))(3)Fe(μ(2)-OAr(F))(2)Fe(OAr(F))(3)], 5. These compounds have been characterized with UV-vis spectroscopy, elemental analysis, Evans method susceptibility, and X-ray crystallography. All-electron, geometry-optimized DFT calculations on four [Ti(IV)(OAr)(4)] and four [Fe(III)(OAr)(4)](-) species (Ar = 2,3,5,6-C(6)Me(4)H, C(6)H(5), 2,4,6-C(6)Cl(3)H(2), C(6)F(5)) with GGA-BP and hybrid B3LYP basis sets demonstrated that, under D(2d) symmetry, π donation from the O 2p orbitals is primarily into the d(xy) and d(z(2)) orbitals. The degree of donation is qualitatively consistent with expectations based on ligand Brønsted basicity and supports the contention that fluorinated phenolate ligands facilitate isolation of nonbridged homoleptic complexes due to their reduced π basicity at oxygen.
authors.affiliation: Chemistry Department, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, USA.
authors.forename: Stefanie A
authors.initials: SA
authors.lastname: Cantalupo
authors.forename: Helen E
authors.initials: HE
authors.lastname: Ferreira
authors.forename: Eman
authors.initials: E
authors.lastname: Bataineh
authors.forename: Annie J
authors.initials: AJ
authors.lastname: King
authors.forename: Montana V
authors.initials: MV
authors.lastname: Petersen
authors.forename: Teresa
authors.initials: T
authors.lastname: Wojtasiewicz
authors.forename: Antonio G
authors.initials: AG
authors.lastname: DiPasquale
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.forename: Linda H
authors.initials: LH
authors.lastname: Doerrer
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010636:Phenols / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D005290:Ferric Compounds; D005296:Ferrous Compounds; D010636:Phenols