Chapter 4 - Jacobs University

Chapter 5
Organoruthenium POM
5.4 Results and discussion
5.4.1 Synthesis and structure
The title polyanion [{K(H 2 O)} 3 {Ru(p-cymene)(H 2 O)} 4 P 8 W 49 O 186 (H 2 O) 2 ] 27- (3) was prepared by a
one-pot reaction of [Ru(p-cymene)Cl 2 ] 2 with P 8 W 48 (10:1 ratio) in aqueous 1M LiOAc/CH 3 COOH
buffer solution at pH 6.0. We isolated 1 in the form of its mixed potassium-lithium salt
K 12 Li 15 [{K(H 2 O)} 3 {Ru(p-cymene)(H 2 O)} 4 P 8 W 49 O 186 (H 2 O) 2 ]·87H 2 O (3a) which was structurally
characterized by single crystal X-ray diffraction. The extra equivalent of tungstate which appears
in 3 is most likely formed in situ by decomposition of a very minor fraction of the P 8 W 48
precursor. Compound 1a has been fully characterized in the solid state by single-crystal XRD,
TGA-DSC, IR and elemental analysis.
Figure 5.3 Combined polyhedral/ball-and-stick representation of 3. The color code is as follows: WO 6
(violet, blue), PO 4 (yellow), Ru (green), O (red), C (black), K (orange). No hydrogens shown for clarity.
Note that the two blue WO 6 octahedra and the two adjacent potassium ions have 50% occupancy each.
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