Reactivity of a (Benzene)Ruthenium(II) Cation on a Di‐lacunary γ‐Keggin‐Type Silicotungstate and Synthesis of a Mono‐(Benzene)Ruthenium(II)‐Attached γ‐Keggin‐Type Silicotungstate

Identifier:  imarina:5131984

Handle: https://hdl.handle.net/20.500.11797/imarina5131984

Authors:  Kikuchi, Masaya; Ota, Hiromi; Lopez, Xavier; Nakaya, Toshimi; Tsunoji, Nao; Sano, Tsuneji; Sadakane, Masahiro

Abstract:
Reaction of a (benzene)Ru2+ complex, [Ru(C6H6)Cl2]2, with a di‐lacunary γ‐Keggin‐type silicodecatungstate, K8[γ‐SiW10O36], at a (C6H6)Ru2+/[γ‐SiW10O36]8- ratio of 1 produces [γ‐SiW10O36Ru(C6H6)]6-. The cesium salt was characterized using experimental and theoretical methods; one (C6H6)Ru2+ moiety is attached through three bridging oxygen atoms of the non‐lacunary site, and the anion is stable in aqueous solution. 1H NMR spectroscopy and high‐resolution electrospray ionization mass spectrometry measurements of the reaction mixture with different (C6H6)Ru2+/[γ‐SiW10O36]8- ratios indicate that the (C6H6)Ru2+ complex first reacts with the three bridging oxygen atoms to form [γ‐SiW10O36Ru(C6H6)]6-, and then react on the terminal oxygen atoms of the lacunary site to form a [γ‐SiW10O36Ru(C6H6)]6- complex, which was reported by the Kortz and Nadjo group.