The hydrogenphosphate complex of (1,5-cyclooctadiene)iridium(I), {[Bu4N][(1,5-COD)Ir center dot HPO4]}(n): Synthesis, spectroscopic characterization, and ES-MS of a new, preferred precursor to HPO42- and Bu4N+ stabilized Ir(0)(n) nanoclusters

Ozkar S., Finke R.

JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol.689, no.3, pp.493-501, 2004 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 689 Issue: 3
  • Publication Date: 2004
  • Doi Number: 10.1016/j.jorganchem.2003.10.038
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.493-501
  • Keywords: hydro-enphosphate-organometallic complexes, synthesis and characterization, electrospray mass spectrometry of organometallics, discrete precursors to phosphate-stabilized nanocluster catalysts, ELECTROSPRAY MASS-SPECTROMETRY, CRYSTAL-STRUCTURE, HYDROGEN PHOSPHATE, CLUSTER COMPLEXES, LIGANDS, PHOSPHODIESTER, PRECATALYSTS, SULFATE
  • Middle East Technical University Affiliated: Yes


The synthesis and characterization of a previously unknown, rare organometallic-phosphate complex, {[Bu4N][(1,5-COD)Ir.HPO4]}(n) (1), is described. Characterization of 1 was accomplished by elemental analysis, electrospray mass spectrometry (ES-MS), and H-1 and C-13 NMR which established the symmetry of the product as at least C-2 or C-5. The ES-MS reveals an interesting, Ir(I) to Ir(III) oxidative process with intense peaks displaying the Ir-191/Ir-193 isotopic distribution patterns expected for the fragments [(1,5-COD)Ir-III(HPO4)(2)](-), [(C8H11)(2)(Ir-III)(2)(PO4)(HPO4)(H2O)](-), and [(C8H11)(2)(Ir-III)(2)(PO4)(HPO4)(H2O)(2)](-). These fragments, in turn, provide evidence for a structure with two HPO42- groups attached to a single Ir, for example ring structures (of at least such C-2 or C-5 symmetry) such as {[Bu4N][(1,5-COD)Ir.HPO4]}(2). Complex 1 is significant since it is known to be the preferred, compositionally precise precursor to the prototype example of a recently discovered class of novel, HPO42- and Bu4N+ stabilized nanoclusters, (Bu4N)(2n)(2n+)[Ir(0)(n).(HPO4)(n)](2n-). Such nanoclusters are being extended, via their analogous hydrogenphosphate-organometallic precursors (1,5-COD)M+ (or 2+)/HPO42- (M = Rh(I), Ru(II), Pt(II)) to their corresponding, catalytically active [M(0)(n).(HPO4)(n)](2n-) nanoclusters. (C) 2003 Elsevier B.V. All rights reserved.