Facile Incorporation of Platinum(IV) into Polyoxometalate Frameworks: Preparation of [H₂Pt^IVV₉O₂₈]⁵⁻ and Characterization by ¹⁹⁵Pt NMR Spectroscopy

Abstract

A new mate for vanadate: The platinum(IV)‐containing polyoxovanadate [H2PtIVV9O28]5− (1) has been synthesized and structurally characterized (see polyhedral representation). The characterization of polyanion 1 in solution by 195Pt NMR spectroscopy is unprecedented in POM chemistry. The facile synthetic procedure with the PtIV precursor H2Pt(OH)6 appears to be a convenient and general methodology for making a large variety of PtIV‐containing polyoxometalates.

NMR Chemical Shifts of Metal Centres in Polyoxometalates: Relativistic DFT Predictions

“…[2,3,5] [a] School of Engineering 5-). In the case of dilacunary polyoxotungstates our calculations confirm the necessity of modelling an ion pair in which a counterion is specifically included in the POM lacuna to attain accurate predictions of the corresponding 183 W NMR spectra.…”

Platinum‐Containing Polyoxometalates

“…2.5) of one of several other platinum-substituted decavanadate species peripherally reported by us, [1] Hill et al have overlooked the fact that the formulation reported here or indeed in any crystal structure is an average over the entire crystal. Stochastic disorder and/or presence of hydrogen atoms (or other atoms) on or close to special positions will inevitably lead to fractional occupancies.…”

“…They draw attention to some perceived problems with our recent paper in this journal [1] reporting the isolation and structural characterization of [H 2 Pt IV V 9 O 28 ] 5À (1); they argue that an anion, a-[SiW 10 Pt…”

Platinum‐Containing Polyoxometalates

“…[5,[12][13][14] Furthermore, terminal metal oxo species exhibit the only multiple noble-metal-oxygen bonds and such species should not exist based on electronic structure arguments. [5,13,14] [11] (cited as reference [12] in reference [1]) the (guanidinium) 8 ({SiW 11 }). First, the infrared spectra of the crystalline guanidinium salts of {SiPt 2 W 10 } prepared using the exact published procedure of Lee et al, [11] and {SiW 11 } are identical (Figure 1 a).…”