Revisiting the Polyoxometalate-Based Late-Transition-Metal-Oxo Complexes: The "Oxo Wall" Stands

TitleRevisiting the Polyoxometalate-Based Late-Transition-Metal-Oxo Complexes: The "Oxo Wall" Stands
Publication TypeJournal Article
Year of Publication2012
AuthorsO'Halloran KP, Zhao CC, Ando NS, Schultz AJ, Koetzle TF, Piccoli PMB, Hedman B, Hodgson KO, Bobyr E, Kirk ML, Knottenbelt S, Depperman EC, Stein B, Anderson TM, Cao R, Geletii YV, Hardcastle KI, Musaev DG, Neiwert WA, Fang XK, Morokuma K, Wu SX, Kogerler P, Hill CL
Journal TitleInorganic Chemistry
Date Published07
Type of ArticleArticle
ISBN Number0020-1669
Accession NumberWOS:000305853600009
Keywordsatom transfer-reactions, bond-stretch isomerism, crystal, heteropolyanion, ligands, MOTION, nmr, reactivity, scale, spectra

Terminal oxo complexes of the late transition metals Pt, Pd, and Au have been reported by us in Science and Journal of the American Chemical Society. Despite thoroughness in characterizing these complexes (multiple independent structural methods and up to 17 analytical methods in one case), we have continued to study these structures. Initial work on these systems was motivated by structural data from X-ray crystallography and neutron diffraction and O-17 and P-31 NMR signatures which all indicated differences from all previously published compounds. With significant new data, we now revisit these studies. New X-ray crystal structures of previously reported complexes K-14[P2W19O69(OH2)] and "K10Na3[Pd-IV(O)(OH)WO(OH2)(PW9O34)(2)]" and a closer examination of these structures are provided. Also presented are the O-17 NMR spectrum of an O-17-enriched sample of [PW11O39](7-) and a careful combined P-31 NMR-titration study of the previously reported "K7H2[Au(O)(OH2)P2W20O20(OH2)(2)]." These and considerable other data collectively indicate that previously assigned terminal Pt-oxo and Au-oxo complexes are in fact cocrystals of the all-tungsten structural analogues with noble metal cations, while the Pd-oxo complex is a disordered Pd(II)-substituted polyoxometalate. The neutron diffraction data have been re-analyzed, and new refinements are fully consistent with the all-tungsten formulations of the Pt-oxo and Au-oxo polyoxometalate species.

URL<Go to ISI>://WOS:000305853600009
Alternate JournalInorg. Chem.