Gas‐Phase Fragmentation Reactions of Keggin‐Type {PW₁₁O₃₉M} (M = Rh, Ir, and Ru) Polyoxometalates as Fingerprints of the Ligands Attached at the Noble Metal Site

Abstract

The gas-phase fragmentation reactions of Keggin-type [PW 11 O 39 MCl] 5-(M = Rh, Ir) polyoxometalates (POMs) featuring chloride terminal ligands have been investigated. Different adducts of the general formulas [PW 11 O 39 MCl + 2cat] 3and [PW 11 O 39 MCl + 3cat] 2-[cat = alkylammonium cations (Me 4 N + , Bu 4 N + ), alkali cations (Na + , K + ) or protons] were subjected to collision-induced dissociation (CID) conditions. The (cat)Cl (cat = H + , Na + or K + ) fragments were released as a common fragmentation pathway and were taken [a]

Catalysis of “outer-phase” oxygen atom exchange reactions by encapsulated “inner-phase” water in {V15Sb6}-type polyoxovanadates

“…ESI-MS experiments range from the clusters' analytical characterisation12 to studies of their solution reactivity13 and to gas-phase experiments aiming at unravelling reaction patterns in the gas phase14 including the activation of small molecules such as methane 15. Mass spectrometry together with isotope exchange reactions can provide profound insight into cluster reactivity as evidenced by elegant studies of Schüth et al on silicate clusters 16.…”

“…In this context, electrospray ionisation mass spectrometry (ESI-MS) has become a valuable tool in oxo-cluster chemistry and a significant body of knowledge has been acquired on the MS investigation of polyoxometallates. 11 ESI-MS experiments range from the clusters' analytical characterisation 12 to studies of their solution reactivity 13 and to gas-phase experiments aiming at unravelling reaction patterns in the gas phase 14 including the activation of small molecules such as methane. 15 Mass spectrometry together with isotope exchange reactions can provide profound insight into cluster reactivity as evidenced by elegant studies of Schüth et al on silicate clusters.…”

Two Ce3+-Substituted Selenotungstates Regulated by N,N-Dimethylethanolamine and Dimethylamine Hydrochloride

“…As is well-known, POMs are hypersensitive to the pH of the medium. The ESI-MS technique can be applied to measure the stability and integrity of POMs in aqueous solution. − Hence, the ESI-MS spectra of 1 and 2 dissolved in different pH water solutions were measured (Figures S5 and S6). The pH of the water solution was regulated using dilute sodium hydroxide and sulfuric acid.…”

Preparation and Structural Characterization of Mono‐Ru‐Substituted α2‐Dawson‐Type Phosphotungstate with a Carbonyl Ligand and Other Ru(CO)‐Substituted Heteropolytungstates

“…Here, we describe the reactions of Ru(acac) 3 [15] We reacted Ru(acac) 3 [16] at 1940 and 1958 cm -1 , respectively. The 31 P NMR spectrum of the reaction mixture shows four peaks [ Figure 4 (a)], whereas the 31 P NMR spectrum of the isolated darkgreen crystal shows two signals at -9.20 and -13.29 ppm with a 1:1 integration ratio typical of mono-Ru-substituted Dawson-type phosphotungstate [ Figure 4 (b)], indicating that a Dawson-type compound in the reaction mixture can be isolated by the addition of acetone and subsequent recrystallization.…”