Chapter 4 - Jacobs University

Chapter 6
U-peroxo-Polyoxometalate
{Ln 4 (H 2 O) 28 [KÌP 8 W 48 O 184 (H 4 W 4 O 12 ) 2 Ln 2 (H 2 O) 10 ] 13- } x (Ln = La, Ce, Pr, Nd), 18 and our group
reported the first transition metal and organoruthenium derivatives,
[Cu 20 Cl(OH) 24 (H 2 O) 12 (P 8 W 48 O 184 )] 24- , 19 [{K(H 2 O)} 3 {Ru(p-cymene)(H 2 O)} 4 P 8 W 49 O 186 (H 2 O) 2 ] 27-
20
and [P 8 W 48 O 184 Fe 16 (OH) 28 (H 2 O) 4 ] 20- . 21
Mialane and coworkers isolated the Cu 20 -azide
derivative [P 8 W 48 O 184 Cu 20 (N 3 ) 6 (OH) 18 ] 24- . 22 Finally, Müller’s group prepared the mixed-valence
dodecavanadium cluster [K 8 Ì{P 8 W 48 O 184 }{V V 4V IV 2O 12 (H 2 O) 2 } 2 ] 24- . 23
Although the 24-tungsto-4-phosphate P 4 W 24 has been known since 1984, 17 its reactivity
towards electrophiles in aqueous solution has remained pretty much unexplored. In 2006, our
group reported the dimethyltin complex [{Sn(CH 3 ) 2 } 4 (H 2 P 4 W 24 O 92 ) 2 ] 28- by using P 4 W 24 as a
precursor. 24 This was the first structural evidence for the elusive P 4 W 24 and at the same time the
first evidence for a lacunary Preyssler ion. To our knowledge, no other structural reports using
the P 4 W 24 precursor have been reported in the literature.
108