Preparation and Structural Characterization of Mono‐Ru‐Substituted α 2 ‐Dawson‐Type Phosphotungstate with a Carbonyl Ligand and Other Ru(CO)‐Substituted Heteropolytungstates

In our previous article ( Dalton Trans. 2008 , 6692–6698) we reported that hydrothermal reaction of a mono‐lacunary Keggin‐type silicotungstate, [SiW 11 O 39 ] 8– , and Ru(acac) 3 (acac: acetylacetonate) for 5–24 h produced a mono‐Ru‐substituted Keggin‐type silicotungstate with a terminal aqua ligand, [SiW 11 O 39 Ru III (H 2 O)] 5– , which was further converted into a carbonyl (CO) derivative, [SiW 11 O 39 Ru II (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, [GeW 11 O 39 Ru II (CO)] 6– and [PW 11 O 39 Ru II (CO)] 5– , and Dawson‐type phosphotungstates, [α 1 ‐P 2 W 17 O 61 Ru II (CO)] 8– and [α 2 ‐P 2 W 17 O 61 Ru II (CO)] 8– , are presented. The desired α 2 ‐isomer of Dawson‐type phosphotungstate, [α 2 ‐P 2 W 17 O 61 Ru II (CO)] 8– , was produced in high purity and was fully characterized by CV, 31 P NMR, 13 C NMR, IR, UV/Vis, elemental analysis, mass spectroscopy, TG‐DTA, TPD‐MS, and single‐crystal structure analysis. On the other hand, Keggin‐type complexes, [GeW 11 O 39 Ru II (CO)] 6– and [PW 11 O 39 Ru II (CO)] 5– , were formed together with their aqua derivatives, [GeW 11 O 39 Ru III (H 2 O)] 5– and [PW 11 O 39 Ru III (H 2 O)] 4– , respectively, and the α 1 ‐isomer of Dawson‐type phosphotungstate, [α 1 ‐P 2 W 17 O 61 Ru II (CO)] 8– , was produced together with the α 2 ‐derivative, as confirmed by CV, IR, mass spectroscopy, and 31 P NMR spectroscopy.