Synthesis and characterization of [PW11O39Ir(H2O)]4-: successful incorporation of Ir into polyoxometalate framework and study of the substitutional lability at the Ir(III) site.

The first Keggin-type heteropolyanion, [PW(11)O(39)Ir(H(2)O)](4-) (1), was synthesized by hydrothermal reaction from two different polytungstate precursors and [IrF(6)](2-). It was isolated as (Bu(4)N)(4)[PW(11)O(39)Ir(H(2)O)] (1a), which was completely characterized by multinuclear (31)P and (183)W NMR, ESI-mass spectrometry and cyclic voltammetry. A rapid screening methodology to ascertain the intrinsic substitutional lability at the Ir site is also presented, based on ESI-MS.

[1]  Y. Geletii,et al.  Structurally characterized iridium(III)-containing polytungstate and catalytic water oxidation activity. , 2009, Inorganic chemistry.

[2]  L. Cronin,et al.  Discovery of heteroatom-"embedded" Te {W18O54} nanofunctional polyoxometalates by use of cryospray mass spectrometry. , 2009, Angewandte Chemie.

[3]  L. Cronin,et al.  Unravelling the complexities of inorganic and supramolecular self-assembly in solution with electrospray and cryospray mass spectrometry. , 2009, Chemical communications.

[4]  V. Fedin,et al.  Unprecedented linking of two polyoxometalate units with a metal-metal multiple bond. , 2009, Inorganic chemistry.

[5]  Gianfranco Scorrano,et al.  Polyoxometalate embedding of a tetraruthenium(IV)-oxo-core by template-directed metalation of [gamma-SiW10O36]8-: a totally inorganic oxygen-evolving catalyst. , 2008, Journal of the American Chemical Society.

[6]  Scott G. Mitchell,et al.  Unravelling the complexities of polyoxometalates in solution using mass spectrometry: protonation versus heteroatom inclusion. , 2008, Journal of the American Chemical Society.

[7]  R. Thouvenot,et al.  Synthesis and characterization of the Keggin-type ruthenium-nitrido derivative [PW11O39{RuN}]4- and evidence of its electrophilic reactivity. , 2007, Journal of the American Chemical Society.

[8]  Karen M. Bloch,et al.  The F/Ph rearrangement reaction of [(Ph3P)3RhF], the fluoride congener of Wilkinson's catalyst. , 2005, Journal of the American Chemical Society.

[9]  A. Bagno,et al.  Microwave Assisted Rapid Incorporation of Ruthenium into Lacunary Keggin-Type Polyoxotungstates: One-step Synthesis, 99Ru, 183W NMR Characterization and Catalytic Activity of [PW11O39RuII(DMSO)]5- , 2000 .

[10]  M. T. Pope,et al.  Rhodium−Carbon Bond Formation in Aqueous Solution. Synthesis, Structure, and Reactivity of the Functionalized Heteropolytungstates, [XW11O39RhCH2COOH]5,6- (X = P, Si) , 1998 .

[11]  M. T. Pope,et al.  Rhodium Derivatives of Lacunary Heteropolytungstates Illustrate Metalloporphyrin Analogies. Reductive Dimerization to Rh2-Linked Keggin Moieties , 1998 .

[12]  O. P. Anderson,et al.  2CH3CN⊂(n-Bu4N)2[{Ir(1,5-COD)}6W4O16]·2CH3CN: A Hybrid Inorganic−Organometallic, Flexible Cavity Host, Acetonitrile−Guest Complex Composed of a [W4O4]n+ Tetratungstate Cube and Six Polyoxoanion-Supported (1,5-COD)Ir+ Organometallic Groups , 1997 .

[13]  B. Yue,et al.  Preparation and Characterization of Keggin Type Polyoxotungstates Containing Palladium or Iridium , 1997 .

[14]  W. Preetz,et al.  Darstellung, Kristallstruktur, spektroskopische Charakterisierung und Normalkoordinatenanalyse von trans‐[PtF2(Py)4](BPh4)2 · 2H2O , 1997 .

[15]  Achim Müller,et al.  Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines , 1991 .

[16]  V. Day,et al.  Niobotungstate, Nb2W4O194- and triphosphate, P3O93-, complexes of (cyclooctadiene)iridium(I): synthesis, structure, and stability of tetra-n-butylammonium salts of {[(C8H12)Ir]5(Nb2W4O19)2}3-, {[(C8H12)Ir]2H(Nb2W4O19)2}5-, and [(C8H12)Ir(P3O9)]2- , 1990 .

[17]  A. Yagasaki,et al.  Synthesis and Structural Characterization of a Polyoxoanion Supported 1,5-Cyclooctadieneiridium(I) Complex, [(η-C8H12)Ir(κ3O-C5Me5TiW5O18)]2− , 1989 .

[18]  H. Gamsjäger,et al.  Preparation and ultraviolet–visible spectrum of hexa-aquairidium(III) , 1976 .

[19]  P. Robinson,et al.  119. Complex fluorides of quadrivalent osmium and iridium and the corresponding free acids , 1958 .

[20]  D. Irvine,et al.  594. A potentiometric study of the chloroiridate–chloroiridite couple , 1957 .