title: Reactions of trivacant Wells-Dawson heteropolytungstates. Ionic strength and Jahn-Teller effects on formation in multi-iron complexes.
abstract: Reaction of alpha-P(2)W(15)O(56)(12-) and Fe(III) in a saturated NaCl solution produces a trisubstituted Wells-Dawson structure with three low-valent metals, alpha-(Fe(III)Cl)(2)(Fe(III)OH(2))P(2)W(15)O(59)(11-) (1). Dissolution of this species into 1 M NaBr (Br(-) is non-coordinating) gives the triaquated species alpha-(Fe(III)OH(2))(3)P(2)W(15)O(59)(9-) (2). Ionic strength values of 1 M or greater are necessary to avoid decomposition of 1 or 2 to the conventional sandwich-type complex, alpha beta beta alpha-(Fe(III)OH(2))(2)Fe(III)(2)(P(2)W(15)O(56))(2)(12-) (3). If the pH is greater than 5, a new triferric sandwich, alpha alpha beta alpha-(NaOH(2))(Fe(III)OH(2))Fe(III)(2)(P(2)W(15)O(56))(2)(14-) (4), forms rather than 3. Like the previously reported Wells-Dawson-derived sandwich-type structures with three metals in the central unit ([TM(II)Fe(III)(2)(P(2)W(15)O(56))(P(2)TM(II)(2)W(13)O(52))],(16-) TM = Cu, Co), this complex has a central alpha-junction and a central beta-junction. Thermal studies suggest that 4 is more stable than 3 over a wide range of temperatures and pH values. The intrinsic Jahn-Teller distortion of d-electron-containing metal ions incorporated into the external sites of the central multi-metal unit impacts the stoichiometry of their incorporation (with a consequent change in the inter-POM-unit connectivity, where POM = polyoxometalate). Reaction of non-distorting Ni(II) with the diferric lacunary sandwich-type POM alpha alpha alpha alpha-(NaOH(2))(2)Fe(III)(2)(P(2)W(15)O(56))(2)(16-) (5) produces alpha beta beta alpha-(Ni(II)OH(2))(2)Fe(III)(2)(P(2)W(15)O(56))(2)(14-) (6), a Wells-Dawson sandwich-type structure with two Ni(II) and two Fe(III) in the central unit. All structures are characterized by (31)P NMR, IR, UV-vis, magnetic susceptibility, and X-ray crystallography. Complexes 4 and 6 are highly selective and effective catalysts for the H(2)O(2)-based epoxidation of alkenes.
authors.affiliation: Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
authors.forename: Travis M
authors.initials: TM
authors.lastname: Anderson
authors.forename: Xuan
authors.initials: X
authors.lastname: Zhang
authors.forename: Kenneth I
authors.initials: KI
authors.lastname: Hardcastle
authors.forename: Craig L
authors.initials: CL
authors.lastname: Hill
mesh_terms: D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D003035:Cobalt / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D005290:Ferric Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry; D008345:Manganese / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012965:Sodium Chloride / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics; D014414:Tungsten / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry
chemical_list: D000475:Alkenes; D005290:Ferric Compounds; D009942:Organometallic Compounds; D003035:Cobalt; D008345:Manganese; D012965:Sodium Chloride; D003300:Copper; D009532:Nickel; D006861:Hydrogen Peroxide; D015032:Zinc; D014414:Tungsten