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

Abstract

AbstractIn our previous article (Dalton Trans. 2008, 6692–6698) we reported that hydrothermal reaction of a mono‐lacunary Keggin‐type silicotungstate, [SiW11O39]8–, and Ru(acac)3 (acac: acetylacetonate) for 5–24 h produced a mono‐Ru‐substituted Keggin‐type silicotungstate with a terminal aqua ligand, [SiW11O39RuIII(H2O)]5–, which was further converted into a carbonyl (CO) derivative, [SiW11O39RuII(CO)]6–, by increasing the reaction time for several days. Here, reactions of Ru(acac)3 with other mono‐lacunary heteropolytungstates for the formation of other mono‐Ru(CO)‐substituted heteropolytungstates, including Keggin derivatives, [GeW11O39RuII(CO)]6– and [PW11O39RuII(CO)]5–, and Dawson‐type phosphotungstates, [α1‐P2W17O61RuII(CO)]8– and [α2‐P2W17O61RuII(CO)]8–, are presented. The desired α2‐isomer of Dawson‐type phosphotungstate, [α2‐P2W17O61RuII(CO)]8–, was produced in high purity and was fully characterized by CV, 31P NMR, 13C NMR, IR, UV/Vis, elemental analysis, mass spectroscopy, TG‐DTA, TPD‐MS, and single‐crystal structure analysis. On the other hand, Keggin‐type complexes, [GeW11O39RuII(CO)]6– and [PW11O39RuII(CO)]5–, were formed together with their aqua derivatives, [GeW11O39RuIII(H2O)]5– and [PW11O39RuIII(H2O)]4–, respectively, and the α1‐isomer of Dawson‐type phosphotungstate, [α1‐P2W17O61RuII(CO)]8–, was produced together with the α2‐derivative, as confirmed by CV, IR, mass spectroscopy, and 31P NMR spectroscopy.